Polymeric surfactants derived from cyclic monomers having pendant fluorinated carbon groups

ABSTRACT

A fluorine containing polymer which acts as a wetting, flow or leveling agent, and has at least one polar group. The polymer has at least one pendant or ether side chain containing from about 1 to about 20 carbon atoms with at least 25% of the hydrogen atoms being replaced by fluorine atoms. The fluorinated polymers unexpectedly impart wetting, flow or leveling properties to a variety of coatings while producing little foam.

CROSS REFERENCE

This application is a continuation of U.S. Ser. No. 10/142,229, filedMay 9, 2002 now abandoned, which is a continuation-in-part of U.S. Ser.No. 09/855,053 filed May 14, 2001 now U.S. Pat. No. 6,660,828.

FIELD OF THE INVENTION

One or more low carbon atom fluorocarbons of usually 7 carbon atoms orless are contained on a polymer generally having polar groups. Thefluorocarbons generally exist as side chains with at least 25% of thehydrogen atoms being replaced by fluorine atoms. The polymer of thepresent invention is found unexpectedly to be an effective wetting, orflow, or leveling agent while producing little foam.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 3,859,253 to Bourat et al. relates to polyoxetanescomprising a plurality of repeating units wherein the chain oxygen atomsof each recurring unit is attached to a chain methylene group of anadjacent recurring unit with, in addition, cross-linking via the otherfree valencies when the polymer contains repeating units.

U.S. Pat. No. 5,068,397 to Falk et al. relates to tris-perfluoroalkylterminated neopentyl alcohols of the formula (R_(f)-E_(n)-X—CH₂)₃CCH₂OHprepared from halogenated neopentyl alcohols and thiols of the formulaR_(f)-E_(n)-SH, amines of the formula R_(f)-E_(n)-NH—R, alcohols of theformula R_(f)-E_(n)-OH, and perfluoro-acids or amides. The alcoholsreact with isocyanates to prepare urethanes; with acids or derivativesto prepare esters or carbonates; with epoxides to form ethers. Further,they may be converted to halide intermediates. The products all containthe residue of at least one R_(f)-neopentyl alcohol containing threeperfluoroalkyl hetero groups.

U.S. Pat. No. 5,674,951 to Hargis et al. relates to coating compositionswhich use a polyoxetane polymer having —CH₂—O—CH₂—R_(f) side chainswhere R_(f) is a highly fluorinated alkyl or polyether. The coatingcompositions use polyisocyanates to create isocyanate terminatedpolymers from the poly(oxetane) and from various polyols from alkyleneoxides or polyester polyols. These can be reacted together to form blockcopolymer structures or can be linked together when the coating iscrosslinked. A preferred method is to use blocked isocyanate groups.Another preferred embodiment is to use the composition as an abrasionresistant coating for glass run channels.

U.S. Pat. No. 5,807,977 to Malik et al. relates to fluorinated polymersand prepolymers derived from mono-substituted oxetane monomers havingfluorinated alkoxymethylene side-chains and the method of making thesecompositions. The mono-substituted fluorinated oxetane monomers havingfluorinated alkoxymethylene side-chains are prepared in high yield bythe reaction of a fluorinated alkoxide with either3-halomethyl-3-methyloxetane premonomers. It also relates to copolymersof oxetane and tetrahydrofuran.

U.S. Pat. No. 5,998,574 to Fishback et al. relates to a polyolcomposition comprising: (A) a polytetramethylene ether glycol, and (2) adifunctional active hydrogen compound-initiated polyoxyalkylenepolyether polyol having a degree of unsaturation of not greater than0.04 milliequivalents per gram of said polyether polyol.

U.S. Pat. No. 6,020,451 to Fishback et al. relates to a polyolcomposition comprising: (A) a polytetramethylene ether glycol, and (2) adifunctional active hydrogen compound-initiated polyoxyalkylenepolyether polyol having a degree of unsaturation of not greater than0.04 milliequivalents per gram of said polyether polyol.

U.S. Pat. No. 6,127,517 to Koike et al. relates to the polymerization ofhexafluoropropene oxide (HFPO) in a polymerization initiator solution ofthe formula: CsCF₂—R_(f)—CF₂OCs wherein R_(f) is a perfluoroalkylenegroup which may have an ether bond in an aprotic polar solvent providedthat the initiator solution is first treated by adding a perfluoroolefinthereto at a sufficient temperature for the removal of protonicsubstances, cesium fluoride and hydrogen fluoride. This simple treatmentrestrains chain transfer reaction, and the process is successful inproducing a difunctional HFPO polymer having a high degree ofpolymerization while suppressing formation of a monofunctional HFPOpolymer.

U.S. Pat. No. 6,168,866 to Clark relates to a curablefluorine-containing coating composition comprising: (i) an amino resin;(ii) an addition fluoropolymer comprising a copolymer of a fluorinatedmonomer having a fluorocarbon group of at least 3 carbons, and anon-fluorinated monomer having a crosslinking group capable of reactingwith said amino resin at elevated temperatures; and (iii) a hardeningagent capable of crosslinking with said amino resin at elevatedtemperatures.

Heretofore, non-polymeric molecules containing fluorinated and polargroups were used as wetting, or flow, or leveling agents; however, manyof these materials have been shown to bioaccumulate thereby greatlylimiting their utility.

SUMMARY OF INVENTION

The partial or fully fluorinated short carbon atom side chain containingpolymers of the present invention unexpectedly have good wetting, orflow, or leveling properties. The types of polymers are numerous andinclude polymers derived from cyclic ethers, poly(acrylates),poly(methacrylates), hydroxyl terminated poly(acrylates) orpoly(methacrylates), polyolefins, polymers derived from vinylsubstituted aromatic monomers such as styrene, polyesters,polyurethanes, polyamides, polyimides, polysiloxanes, and the like withpolyoxetane being preferred. The polymers desirably have at least onegroup that is polar which can be an anionic group, a cationic group, ora nonionic group. The polymer can also be amphoteric containing bothanionic and cationic groups.

Furthermore, the polymers of the present invention can be caused toreact with another compound, or monomer or with another polymer toimpart effective wetting, or flow, or leveling properties to a coatingprepared therefrom. Alternatively, the polymers of the present inventioncan be used as an additive with other polymers, copolymers,compositions, etc. to provide improved wetting, or flow, or levelingproperties. Compared to molecules used typically as wetting, or flow, orleveling agents, the materials set forth in the present invention haverelatively little propensity to cause foaming or surface defects withina broad concentration range. This is often a desirable attribute of awetting, flow, or leveling agent.

The invention further relates to nonfluorinated oxetane monomers; oroligomers, polymers, or copolymers thereof generally having pendantalkoxy groups. Such monomers can be polymerized in the presence offluorinated oxetane monomers to produce statistical copolymers thereof.Moreover, block copolymers of the alkoxy oxetanes and the fluorinatedoxetanes can be made.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 and 2 provide a description of preparation of the compounds ofthe present invention on a commercial scale with regard to a Poly-3-FOXpolymer containing polar end groups of ammonium sulfate.

DETAILED DESCRIPTION OF THE INVENTION

The fluorinated short carbon chain compounds of the present inventionare generally located on polymers as side chains thereof. Thesepolymers, which contain one or more polar groups are generallydispersible or soluble in water and various hydrocarbon solvents andunexpectedly function as wetting, or flow, or leveling agents providinggood optical properties to a coating such as high gloss and gooddistinctness of image, and thus can be blended with a wide variety ofsolutions, waxes, polishes, coatings, blends and the like.

Polymers of the present invention contain fluorinated carbon groupsgenerally represented by the formula R_(f).The R_(f) groups can be partof the monomer which is reacted to form the polymer or they can bereacted with an already formed polymer. Alternatively, a polymercontaining a R_(f) group such as a fluorinated polyoxetane can bereacted with a polymer or monomer to form a copolymer which thuscontains a plurality of pendant short chained R_(f) groups thereon.Examples of a non-R_(f) containing copolymer portion are various cyclicethers, various polyesters, various acrylic polymers, variouspolysiloxanes, various polyamides, various polyurethanes, and variouspolymers made from vinyl substituted aromatic monomers.

A wide variety of fluorine-containing polymers can be utilized asgenerally set forth by the following description:

The polymer can be comprised of repeat units (with repeat units beinggreater than or equal to 2) of a variety of monomers including cyclicethers, acrylates, olefins and vinyl moieties. The most preferredmonomers are cyclic ethers (including fluorinated cyclic ethers such asthose based on hexafluoropropylene oxide) such as oxetanes, andoxiranes. Other preferred monomers include acrylates, vinyls includingstyrenics, silanes, and siloxanes, as well as polyester formingmonomers, polyamide forming monomers, polyimide forming monomers, andpolyurethane forming monomers. The polymer may be of the copolymer typecomprised of, but not limited to, the aforementioned monomers. Thecopolymer may be of the statistical or block type. The average degree ofpolymerization should be at least 2 as to about 100 or 200, andpreferably from 2 to about 10 or 20, or 30.

The polymer may contain more than one R_(f) type group and the types ofR_(f), independently, can be the same or different and are fluorinatedalkyl groups such as a linear alkyl group having a main chain of about 7carbon atoms or less, desirably from about 1 to about 5 or 6 carbonatoms, and preferably 2, 3, or 4 carbon atoms. The R_(f) alkyl group canbe branched. When branched, the longest chain is composed of 7 carbonatoms or less with each branch containing a maximum total of 3 carbonatoms or less. R_(f) whether linear or branched has at least one carbonatom bonded to at least one fluorine atom. The total amount of fluorineatoms in each R_(f) group is generally at least 10% or 25%, desirably atleast 50% or 75%, and preferably at least 80%, 85%, 90%, or 95%, or even100% (perfluorinated) of the non-carbon atoms with any remainingnon-carbon atoms or nonfluorine atoms being H, or I, or Cl or Br.

The pendant or side chain R_(f) group can be present on all the monomerscomprising the polymer or on a selected few with a preferable range ofabout 50 to 100% of monomers comprising the polymer containing a pendantor side chain R_(f) group. A preferred polymer contains one R_(f) groupper repeat unit. The R_(f) group can be bonded directly to the polymer,or desirably is covalently bonded through another linking moiety orgroup bonded to the polymer such as a hydrocarbyl, a sulfonyl, an ester,an alkyl sulfide, or the like. A desired moiety is alkyl ether such as—CH₂—O—(CH₂)_(n)—  (Formula 1)where n is from about 1 to about 6 with 1 or 2 being preferred.

The various polymers or copolymers of the present invention desirablyhave polar groups covalently bonded thereto in order to render themsoluble in water or in a solvent. Examples of polar groups covalentlybonded to the polymer include anionic groups such as —CO₂ ⁻(Carboxylate), —SO₃ ⁻ (Sulfonate), —OSO₃ ⁻ (Sulfate), —OPO₃ ⁻(Phosphate), and —ONO₂ ⁻ (Nitrate). Cationic counterions groupsassociated with the just noted anionic polar groups include Li⁺(lithium), Na⁺ (sodium), K⁺ (potassium), Cs⁺ (cesium) and ammonium saltsof the general formula, NH_(4−X)R_(X) ⁺ where R is typically ahydrocarbyl radical (e.g. a hydrocarbon radical) having from 1 to 18carbon atoms and X is 0 to 3, or a quaternary ammonium salt. where x=4.

Cationic polar groups covalently bonded to the polymer includeNH_(4−x)R_(x) ⁺ (Ammonium), or a quarternary ammonium and PH_(4−x)R_(x)⁺ (Phosphonium) where X is as noted above. Anionic counterions groupsconnected to said cationic polar groups include F⁻ (fluoride), Cl⁻(chloride), Br⁻ (bromide), I⁻ (iodide), and BF₄ ⁻ (tetrafluoroborate).

Nonionic polar groups include various polyethers having from 1 to about100 and preferably from about 2 to about 25 repeat units (n) include—O—(CH₂CH₂O)_(n)—H (poly(ethylene oxide)), —O—(CH(CH₃)CH₂O)_(n)—H(poly(propylene oxide)), various polyether copolymers, carbonyl,carboxyl, nitrile, thiol, or cyano but exclude

hydroxyl groups.

Naturally, when a cationic polar group is utilized, it is utilized inconjunction with an anion to form a cation-anion salt, and converselywhen an anion end group is utilized it is utilized in conjunction with acation end group to form an anion-cation salt.

The type of polar group bonded covalently to to the polymer can also beof a mixed anionic/cationic type forming an amphoteric-type polymer.Examples include covalent bonded cationic amine groups and anionicsurfactants such as set forth in McCutheon's Volume 1: Emulsifiers &Detergents, North American Edition, The Manufacturing ConfectionerPublishing Co., Glen Rock, N.J., 1999, hereby fully incorporated byreference.

Preferably, the polar group(s) are covalently bonded to the end(s) ofthe polymer; however, the polar group(s) can be covalently bonded at anylocation along the polymer chain (backbone). The number of polar groupsbonded covalently to the polymer can be 1 to about 10 and preferablyabout 2.

The polar groups can be added by (i) end groups introduced throughpolymerization (from initiators or chain transfer agents), (ii)modification of aforementioned end groups in (i), (iii) specificreactions on the polymer such as grafting (examples are photografting,radiation grafting and oxidation), (iv) addition reactions (such as thatproduced by condensation of a polar group-containing isocyanate with ahydroxyl group on the polymer), (v) substitution or metathesis (forexample, alkyl halide displacement with AgBF₄), and (vi) preferably,esterification of a hydroxyl group with sulfuric acid. Such reactionsare known to the art and to the literature.

Types of Polymers or Copolymers Containing Non-Backbone Pendant R_(f)Groups

A preferred class of polymers are those derived from cyclic ethersgenerally containing from 2 to 5 carbon atoms in the ring and optionallysubstituted alkyl groups thereon containing from 1 to about 20 carbonatoms. Examples of such cyclic ethers include oxirane (epoxy)functionality such as epichlorohydrin, ethylene oxide, butylglycidylether, and perfluorooctyl propylene oxide as well as alkylsubstituted oxiranes having from 1 to about 20 carbon atoms or mixturesthereof; monomers having a 4-membered cyclic ether group such asoxetane, 3,3-bis(chloromethyl)oxetane, 3,3-bis(bromomethyl)oxetane, and,3,3-bromo methyl(methyl)oxetane; monomers having a 5 membered cyclicether group such as tetrahydrofuran, tetrahydropyran, and2-methyltetrahydrofuran; and the like. Still other suitable monomersinclude 1,4-dioxane, 1,3-dioxane and 1,3-dioxalane as well as trioxaneand caprolactone. A preferred polymer is derived from fluorosubstitutedshort carbon chain oxetane monomers as will be more fully discussedhereinbelow.

Another class of preferred polymers include the various acrylic polymerssuch as for example, the various poly(alkyl acrylates) or the variouspoly(alkyl methacrylates) wherein the alkyl portion has from 1 to 18carbon atoms with 1 to 4 carbon atoms being preferred and wherein the“meth” group can be substituted by a C₂ to C₄ alkyl. Still othersuitable acrylic polymers include the various hydroxyl substitutedpoly(alkyl acrylates) and hydroxy substituted poly(alkyl methacrylates)wherein the alkyl group is as noted immediately above. Such polymersgenerally have from about 2 to about 100 repeat units and desirably fromabout 2 to about 10 or 20 or 30 repeat units. The preparation of suchacrylic polymers is known to the literature and to the art. Example ofsuitable acrylate monomers include ethyl acrylate, propyl acrylate,butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate,nonyl acrylate, decyl acrylate, phenyl acrylate, nonylphenyl acrylate,ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexylmethacrylate, methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethylacrylate, butoxyethyl acrylate, ethoxypropyl acrylate,2(2-ethoxyethoxy)ethyl acrylate, and the like. Especially preferredacrylate monomers include butyl acrylate, 2-ethylhexyl acrylate, ethylacrylate, and the like. Hydroxyl alkyl acrylates and methacrylatesinclude hydroxyethyl and hydroxy propylacrylates and methacrylates, andthe like, and are also preferred. Examples of still other acrylates areset forth in U.S. Pat. No. 5,055,515, hereby fully incorporated byreference.

Still another class of polymers are those derived from vinyl substitutedaromatics having a total of from about 8 to about 12 carbon atoms suchas styrene, alpha-methyl styrene, vinyl pyridine, and the like, andcopolymers thereof such as those made from conjugated dienes having from4 to about 12 carbon atoms such as butadiene, isoprene, and the like.The R_(f) group is generally located on the ring compound. Such polymerscan generally have from about 2 to about 100 and desirably from about 2to about 10 or 20 or 30 repeat units. The preparation of such polymersis known to those skilled in the art as well as to the literature.

The polymer can also be a polyester. Polyesters are generally made bythe condensation reaction of one or more dicarboxylic acids, containinga total of from about 2 to about 12 carbon atoms and preferably fromabout 3 or 4 to about 10 carbon atoms and include aliphatic as well asaromatic acids, with glycols or polyols having a total of from about 2to about 20 carbon atoms. Polyesters can also be made by the ringopening polymerization of cyclic esters having from 4 to about 15 carbonatoms such as caprolactone, and the like. While numerous types ofpolyesters exist, such as set forth herein below, preferred polyestersinclude poly(ethylene terephthalate), poly(butylene terephtalate), andthe like. The preparation of polyesters is well known to the art and tothe literature.

The polyamides constitutes another class of polymers which can beutilized. The polyamides are made from cyclic amides having a total offrom about 4 to about 20 carbon atoms such as polyamide 4(polybutyrolactam), polyamide 6 (polycaprolactam), polyamide 12(polylauryl lactam), or polyamides made by the condensation reaction ofa diamine monomer having a total of from about 4 to about 15 carbonatoms with a dicarboxylic acid having from about 4 to about 15 carbonatoms such as polyamide 6,6 (a condensation product of adipic acid andhexamethylenediamine), polyamide 6,10 (a condensation product of sebacicacid and hexamethylenediamine), polyamide 6,12, polyamide 12,12, and thelike with polyamide 6,6, and polyamide 6,12, being preferred. Suchpolyamides often have from about 2 to about 100 and desirably from about2 to about 10 or 20 or 30 repeat units. The preparation of suchpolyamides is well known to the art and to the literature. Examples ofthe above polyamides as well as others are set forth in U.S. Pat. No.5,777,033, which is hereby fully incorporated by reference.

The polysiloxanes still constitute another class of polymers which canbe utilized in the present invention. The polysiloxanes are generallymade from dihydroxysilane which react with each other by dehydration anddehydrochlorination. The side groups of the monomers are generally analkyl having from 1 to about 20 carbon atoms. The number of repeatgroups of the polysiloxanes is generally from about 2 to about 100 anddesirably from about 2 to about 10 or 20 or 30. The preparation of thepolysiloxanes is well known to the art and to the literature. Examplesof suitable polysiloxanes are set forth in U.S. Pat. No. 4,929,664,which is hereby fully incorporated by reference.

The preparation of polyurethanes generally proceed in a stepwise manneras by first reacting a hydroxyl terminated polyester or polyether with apolyisocyanate such as a diisocyanate and optionally, subsequently chainextending and/or crosslinking the same. The polyether monomers of theintermediate can generally have from 2 to about 6 carbon atoms whereasthe polyester intermediates can be made from diols and dicarboxylicacids as noted herein above with regard to the preparation of thevarious polyesters. Suitable diisocyanates generally have the formulaR(NCO)_(x) where X equals 2, 3 or 4 with 2 being preferred. R can be analiphatic, an aromatic, or combinations thereof having from about 4 toabout 20 carbon atoms. Such polyurethanes generally have from about 2 toabout 100 and desirably from 2 to about 10 or 20 or 30 repeat units. Thepreparation of polyurethanes are well known to the art and to theliterature. Examples of suitable polyurethanes are set forth in U.S.Pat. No. 4,975,207, which is hereby fully incorporated by reference.

Polyfluorooxetanes

As noted above, desired fluorine containing polymers are those whereinthe repeat units are obtained from cyclic ethers. Polymerization of suchethers generally proceeds by a cationic or an anionic mechanism. Adesired fluorine containing polymer of the present invention is anoxetane polymer containing fluorinated side chains. The monomers as wellas the polyoxetane oligomers, polymers, or copolymers can be prepared ina manner as set forth herein below, and also according to the teachingsof U.S. Pat. Nos. 5,650,483; 5,668,250; 5,668,251; and 5,663,289, herebyfully incorporated by reference. The oxetane monomer desirably has thestructure

which when polymerized will have repeat units:

wherein as noted above, n is an integer from 1 to about 3 or to about 6and R_(f), independently, on each monomer is a linear or branched,unsaturated, or preferably saturated alkyl group of 1 to about 7, orabout 10, or about 15, or about 20 carbon atoms with a minimum of 25,50, 75, 80, 85, 90 or 95, or preferably perfluorinated i.e. 100 percentof the H atoms of said R_(f) being replaced by F, and optionally up toall of the remaining H atoms being replaced by I, Cl or Br. When Rf isdesirably a short chain, and has from 1 to about 5 or 6 carbon atoms andpreferably contains 2, 3, or 4 carbon atoms. R_(f) can either contain alinear alkyl group or a branched alkyl group. When it is a branchedgroup, the main chain contains from 1 to 7 carbon atoms and each branchchain can contain up to 3 carbon atoms as well. R is hydrogen, or analkyl from 1 to 6 carbon atoms with methyl or ethyl being preferred.

Preferably, the R_(f) group is present on the monomer used to preparethe polymer, but the R_(f) group can be added after the polymer isformed. For example, a typical reaction scheme involves the condensationof a commercially available R_(f) alcohol with a carboxylic acid grouppendant or side chain on the polymer backbone.

The polymerization of the various monomers are usually conducted in thepresence of an inert solvent, either hydrocarbon or a halogenatedsolvent containing from 1 to about 6 carbon atoms with specific examplesincluding methylene chloride, carbon tetrachloride, trichloroethylene,chlorobenzene, dichloroethane, and the like. Polymerization is conductedin the presence of a Lewis catalyst such as complexes of borontrifloride, for example BF₃.etherate and BF₃.THF, BF3.THPYRAN,phosphorus pentafluoride, antimony pentafluoride, zinc chloride,aluminum bromide, and the like with BF₃.THF being preferred. Suitableinitiators are mono or polyhydroxy alcohols containing carbon-fluorinebonds or carbon-hydrogen bonds or combinations thereof and having from 2to about 5 carbon atoms such as ethylene glycol, butane-1,4-diol,propylene glycol, isobutane-1,3-diol, pentane-1,5-diol, pentaerythritol,trimethylolpropane, and the like, or methanol, etc.

The above polymers derived from the noted oxetane monomers generallyhave the structure set forth in formulas 5A and 5B (MOX) if amonoalcohol initiator is utilized or have the structure as set forth informulas 3A and 3B, if a diol initiator is utilized

where n, R_(f), and R are as described above. As the DP of the polymerincreases, the probability increases that the polymer will initiate onboth sides of the R¹ group of the alcohol initiator and thus the rightside of Formulas 3A and 3B will be a mirror image of the left sideexcept that the DP of each side may not be equal. R¹ is an alkyl havingfrom 1 to about 18 carbon atoms and is generally derived from a diolused in preparing the polymer.As noted above, polymers of formulas 3A, 3AA, 3B, and 3BB are obtainedby cationic polymerization.

The average degree of polymerization (DP) of polyoxetane (polymer) ofthe fluorinated polyoxetanes is generally from about 1 to about 500,desirably from about 2 or 3 to about 50 or 100, and preferably fromabout 4 to about 10, 20, or 30.

While the following representative examples relate to the preparation ofspecific FOX (fluorooxetane) monomers, (i.e. mono 3-FOX, mono 7-FOX, andbis 3-FOX). Other mono or bis FOX monomers can be prepared in a similarmanner as set forth in U.S. Pat. Nos. 5,650,483; 5,668,250; 5,668,251;and 5,663,289, herein fully incorporated by reference.

EXAMPLE M1 Preparation of 3-FOX Monomer3-(2,2,2-Trifluoroethoxymethyl)-3-Methyloxetane

Synthesis of the 3-FOX oxetane monomer is performed as follows:

A dispersion of 50 weight percent (2.8 grams, 58.3 mmol) sodium hydridein mineral oil, was washed twice with hexanes and suspended in 35milliliters of dimethyl formamide. Then, 5.2 grams (52 mmol) oftrifluoroethanol was added and the mixture was stirred for 45 minutes. Asolution of 10.0 grams (39 mmol) of 3-hydroxymethyl-3-methyloxetanep-toluenesulfonate in 15 milliliters of dimethyl formamide was added andthe mixture was heated at 75° C.–85° C. for 20 hours, when ¹H MNRanalysis of an aliquot sample showed that the starting sulfonate hadbeen consumed.

The mixture was poured into 100 milliliters of ice water and extractedwith 2 volumes of methylene chloride. The combined organic extracts werewashed twice with water, twice with 2 weight percent aqueoushydrochloric acid, brine, dried over magnesium sulfate, and evaporatedto give 6.5 grams of 3-(2,2,2-trifluoroethoxymethyl)-3-methyloxetane asan oil containing less than 1 weight percent dimethyl formamide. Theyield of this product was 90 percent. The oil was distilled at 30° C.and 0.2 millimeters mercury pressure to give 4.3 grams of analyticallypure 3-FOX, corresponding to a 60 percent yield. The analyses of theproduct were as follows: IR (KBr) 2960–2880, 1360–1080, 990, 840 cm⁻¹;¹H NMR δ 1.33 (s, 3H), 3.65 (s, 2H), 3.86 (q, J=8.8 Hz, 2 H), 4.35 (d,J=5.6 Hz, 2 H), 4.51 (d, J=5.6 Hz, 2 H); ¹³C NMR δ 20.72 39.74, 68.38(q, J=40 Hz), 77.63, 79.41, 124 (q, J=272 Hz). The calculated elementalanalysis for C₇H₁₁F₃O₂ is: C=45.65; H=6.02; F=30.95. The experimentalanalysis found: C=45.28; H=5.83; F=30.59.

EXAMPLE M2 Preparation of 7-FOX Using PTC Process3-(2,2,3,3,4,4,4-Heptafluorobutoxymethyl)-3-Methyloxetane

A 2 L, 3 necked round bottom flask fitted with a reflux condenser, amechanical stirrer, a digital thermometer and an addition funnel wascharged with 3-bromomethyl-3-methyloxetane (351.5 g, 2.13 mol),heptafluorobutan-1-ol (426.7 g, 2.13 mol), tetrabutylammonium bromide(34.4 g) and water (85 mL). The mixture was stirred and heated to 75° C.Next, a solution of potassium hydroxide (158 g, 87% pure, 2.45 mol) inwater (200 mL) was added and the mixture was stirred vigorously at80°–85° C. for 4 hours. The progress of the reaction was monitored byGLC and when GLC analysis revealed that the starting materials wereconsumed, the heat was removed and the mixture was cooled to roomtemperature. The reaction mixture was diluted with water and the organiclayer was separated and washed with water, dried and filtered to give566 g (94%) of crude product. The crude product was transferred to adistillation flask fitted with a 6 inch column and distilled as follows:

Fraction #1, boiling between 20° C.–23° C./10 mm-Hg, was found to be amixture of heptafluorobutanol and other low boiling impurities, wasdiscarded;

Fraction #2, boiling between 23° C. and 75° C./1 mm-Hg, was found to bea mixture of heptafluorobutanol and 7-FOX, was also discarded; and

Fraction #3, boiling at 75° C./1 m m-Hg was >99% pure 7-FOX representingan overall yield of 80.2%

NMR and GLC data revealed that 7-FOX produced by this method wasidentical to 7-FOX prepared using the sodium hydride/DMF process.

Example M3 relates to the preparation and properties of3,3-bis(2,2,2-trifluoroethoyxmethyl)oxetane (B3-FOX).

EXAMPLE M3

Sodium hydride (50% dispersion in mineral oil, 18.4 g, 0.383 mol) waswashed with hexanes (2×) and was suspended in DMF (200 mL). Thentrifluoroethanol (38.3 g, 0.383 mol) was added dropwise over 45 minwhile hydrogen gas was evolved. The mixture was stirred for 30 min and asolution of 3,3-bis-(hydroxymethyl)oxetane di-p-toluenesulfonate (30.0g, 0.073 mol) in DMF (50 mL) was added. The mixture was heated to 75° C.for 64 h when ¹H NMR analysis of an aliquot showed that the startingsulfonate had been consumed. The mixture was poured into water andextracted with methylene chloride (2×). The combined organic extractswere washed with brine, 2% aqueous HCl, water, dried (MgSO₄), andevaporated to give 17.5 g (100%) of3,3-bis-(2,2,2-trifluoroethoxymethyl)oxetane as an oil containing DMF(<1%). The oil was purified by bulb-to-bulb distillation at 42° C.–48°C. (10.1 mm) to give 15.6 g (79%) of analytically pure B6-FOX, colorlessoil: IR (KBr) 2960–2880, 1360–1080, 995, 840 cm⁻¹; ¹H NMR δ 3.87 (s 4H),3.87 (q, J=8.8 Hz, 4H), 4.46 (s, 4H); ¹³C NMR δ 43.69, 68.62 (q, J=35Hz), 73.15, 75.59, 123.87 (q, J=275 Hz); ¹⁹F NMR δ −74.6(s). Anal.Calcd, for C₉H₁₂F₆O₃; C, 38.31; H, 4.29; F, 40.40. Found: C, 38.30; H,4.30; F, 40.19.

EXAMPLE M4 Anhydrous Preparation of 9-FOX Monomer

Weight (S × Mole Material Ratio) g MW mmoles Ratio Scalenonafluorohexanol 1000 1000.00 264.09 3786.59 1.00 BrMMO 656.11 165.023975.91 1.05 18-crown-6 25.00 322.37 77.55 0.020 KOH (86%) 271.71 56.104165.25 1.10 5% ammonium 615.70 18.01 34186.56 9.03 chloride Water588.10 18.01 32654.08 8.62 Theoretical Yield, (g) 1311.1 Expected Yield,983.3 low (g) Expected Yield, high 1245.5 (g) Solids Loading, % 67.1 mlVolume after KOH 1,440.8 addn. Volume after quench 2056.5 Volume afterphase 1185.5 split Volume after wash 1773.6A 3 liter 3-necked round-bottomed flask was equipped with a mechanicalstirrer, nitrogen inlet and outlet, temperature probe, dean-stark trap,and reflux condenser. Nonafluorohexanol (1000 grams, 3.78 moles), BrMMO(656.11 grams, 3.97 moles), 18-crown-6 (25.00 grams) and 200 ml hexanewere added, and the solution was allowed to heat to 79° C. Ground solidPotassium hydroxide (271.71 grams, 86%, 4.16 mmol) was added over 90minutes, while removing water using the dean stark trap. The reactionwas allowed to stir for 2 hours, while water was removed continuously.After 2 hours, 43.53 grams of water had been remove, or 64%, and thereaction was short on BrMMO, so 65 g (7% additional) and 24.7 gramspotassium hydroxide (0.1 equivalents) was added. After an additional 20minutes, 60.21 grams of water, or 88% had been removed, so the reactionwas filtered to remove salts, and washed with water. The hexane monomersolution was distilled under vacuum, 27.5 in Hg, 60° C.–120° C.monomer-BrMMO-nonafluorohexanol azeotrope, 9-FOX monomer 125° C. 983.25grams of 9-FOX monomer, 75% yield.

A copolymer of two or more FOX monomers can be synthesized to producedesirable products. Additionally, copolymers with non-fluorinated cyclicethers can be prepared, preferably with oxetane and/or tetrahydrofuran(THF) monomers.

As noted, preparation of polymers or copolymers from the fluorinatedoxetane monomers described herein can be made in accordance with U.S.Pat. Nos. 5,650,483; 5,668,250; 5,668,251; or 5,663,289; hereby fullyincorporated by reference.

EXAMPLE P1 Homopolymerization of 3-FOX 3-(2,2,2-Trifluoroethoxymethyl)-3-methyloxetane

A solution of 34.3 milligrams (0.38 mmol) of butane-1,4-diol and 109.7milligrams (0.77 mmol) of boron trifluoride etherate in 4 grams ofmethylene chloride was stirred at ambient temperature for 15 minutesunder nitrogen in a dry polymerization flask. The solution was cooled to1.5° C. and a solution of 1.20 grams (6.52 mmol) of3-(2,2,2-trifluoroethoxymethyl)-3-methyloxetane in 1.3 grams ofmethylene chloride was added. The resultant solution was stirred for 5hours at 1°–2° C. at which time ¹H NMR analysis of an aliquot indicatedthat the starting oxetane had been consumed. The solution was warmed toambient temperature and quenched with water. The organic layer waswashed with brine, 2 weight percent aqueous hydrochloric acid, andevaporated to give 1.053 grams ofpoly-3-(2,2,2-trifluoroethoxymethyl)-3-methyloxetane as an oil,corresponding to a 88 percent yield. The polymer analyses were: DSC Tg−45° C., decomposition temperature was greater than 200° C.; GPCM_(n)=7376, M_(w)=7951, polydispersity 1.08, inherent viscosity 0.080dL/g; Equivalent Weight by ¹H NMR=6300; ¹H NMR δ 0.95 (s, 3H), 3.26 (m,4H), 3.52 (s, 2H) 3.84 (q. 2H); ¹³C NMR δ 17.57, 42.09, 69.30 (q, J=33Hz), 74.42, 75.90, 125.18 (q, J=280 Hz).

EXAMPLE P2a-3-FOX and P2b-5-FOX Synthesis ofpoly(3-trifluoroethoxymethyl-3-methyloxetane), 2a andpoly(3-pentafluoropropoxymethyl-3-methyloxetane)2b

A three-necked, 125 mL jacketed vessel with heater/chiller bath,thermometer, stir bar, condenser, addition funnel and inert gas inletand outlet is charged with dried neopentyl glycol (329.92 g, 3.17 mol),BF₃·THF (177.26 g, 1.27 mol) catalyst and CH₂Cl₂ (1.86 Kg, 21.84 mol)solvent. The neopentyl glycol was dried by dissolution in toluene andremoving solvent under reduced pressure. The initiator and catalystsolution was allowed to stir for 30 minutes at room temperature under apositive pressure nitrogen purge. Monomer 2a (3.50 Kg, 19.01 mol) wasthen added to the catalyst/initiator solution at a rate ≈50 g/min usinga pump while maintaining the reaction temperature at 35±10° C. Thereaction was allowed to stir for 2 hours. Extra CH₂Cl₂ was added (2.8Kg, 32.97 mol). Residual BF₃·THF was removed by washing with 2.5 wt %sodium bicarbonate and a water rinse at 40° C. Solvent was then removedunder reduced pressure at 80° C. Polymer 2a was obtained as a clear,viscous liquid in 95%+ yield. Degree of polymerization was determinedusing ¹H NMR spectroscopic analysis and found to be 7. Polydispersitywas determined using GPC and found to be 1.54. Polymer 2b was preparedsimilarly in 95%+% yield. For 2a: ¹H NMR (CDCl₃) □: 0.86–0.9{tilde over(2)}CH₃, 3H), 3.20 (backbone-CH₂—, 4H), 3.43–3.44 (—CH₂O—, 2H),3.81–3.93 (—OCH₂—, 2 H). ¹³C N MR (CDCl₃) □: 17.1–17.3 (—CH₃), 41.0–41.4(backbone-C—), 69.0 (—OCH₂—, q, J₁₉ _(F-) ₁₃ _(C) =43 Hz), 75.3–75.5(ring-CH₂—), 76.0 (—CH₂O—), 124.1 (—CF₃, q of t, J₁₉ _(F-) ₁₃ _(C) =350Hz, J₁ _(H-) ₁₃ _(C) =6.3 Hz). For 2b: ¹H NMR (CDCl₃) □□. 0.86–0.9{tildeover (2)}CH₃, 3H), 3.20 (backbone-CH₂—, 4H), 3.43–3.44 (—CH₂O—, 2H),3.81–3.93 (—OCH₂—, 2H). ^(—)C NMR (CDCl₃) □: 17.0–17.3 (—CH₃), 41.0–41.4(-backbone-C—), 68.2 (—OCH₂—, d of t, J₁₉ _(F-) ₁₃ _(C) =6.3 and 31 Hz),75.5 (—CH₂O—), 73.8–74.1 (backbone-CH₂—), 113.2 (—CF₂—, t of q, J₁₉_(F-) ₁₃ _(C) =50.2 and 352 Hz), 118.8 (—CF₃, q of t, J₁₉ _(F-) ₁₃ _(C)=50.2 and 314 Hz).

EXAMPLE P3 Synthesis of Poly-9-FOX diol, DP 4

Weight Mole Compound (S × Ratio) G MW Moles Ratio δ ml Scale 9-FOX 500.0500.000 348.21 1.44 20.00 1.150 434.8 Methylene Chloride 265.000 84.933.12 43.46 1.330 199.2 Neopentyl Glycol 37.388 104.15 0.36 5.00 1.01736.8 BF₃THF 10.044 139.90 0.07 1.00 1.268 7.9 Methylene Chloride 400.00084.93 4.71 65.60 1.330 300.8 5% sodium bicarbonate 250.00 84.01 0.1492.07 1.000 250.0 Water 425.000 18.01 23.60 328.68 1.000 425.0 Desired Dp4 Theoretical Yield (g) 542.56 Expected Yield, Low (g) 488.31 ExpectedYield, High 515.44 (g) Solids Loading, % 66.78% Max wt % BF3THF 1.85%(incorporated as THF) ml Initial Volume 678.71 Volume after quench,1404.47 ml Volume after wash, ml 1404.47A 2 liter 3-necked reaction flask equipped with a magnetic stirrer,Monomer addition funnel, nitrogen inlet and outlet, temperature probeand reflux condenser was allowed to equilibrate at 25° C. The reactorwas charged with 265 grams of methylene chloride, neopentyl glycol(37.39 g, 360 mmol), and boron trifluoride tetrahydrofuran complex(10.04 gl, 71.76 mmol). The reaction mixture was allowed to stir for 30minutes. 9-fox monomer (500 grams, 1,436 mmol) was added over 1 hour.The temperature reached 31.2 with no induction period. The temperaturereached a maximum of 37° C. The reaction was allowed to stir for 2hours. Additional methylene chloride was added (400 grams) and thesolution was then washed with 250 ml 5% sodium bicarbonate and 425 mlwater to remove the boron trifluoride tetrahydrofuran complex. Thesolution was then dried with magnesium sulfate, and the solvent wasremoved. PolyFOX N Dp 4.2 (513.1 grams) was isolated.

While a polyoxetane homopolymer is preferred, optionally a copolymerderived from one or more different monomers can be used. The polyoxetanecopolymer can be made from comonomers such as cyclic ethers having totalof from 2 to about 5 carbon atoms in the ring, for example an epoxy(oxirane) functionality such as epichlorohydrin, propylene oxide,ethylene oxide, butyl glycidylether, and perfluorooctyl propylene oxideas well as alkyl substituted oxiranes having from 1 to about 20 carbonatoms or mixtures thereof; monomers having a 4-membered cyclic ethergroup such as 3,3-bis(chloromethyl)oxetane, 3,3-bis(bromomethyl)oxetane,and, 3,3-bromo methyl(methyl)oxetane; monomers having a 5 memberedcyclic ether group such as tetrahydrofuran, tetrahydropyran, and2-methyltetrahydrofuran; and the like. Still other suitable monomersinclude 1,4-dioxane, 1,3-dioxane and 1,3-dioxalane as well as trioxaneand caprolactone. The number of alkyl substituted carbon atomssubstituted on any ring carbon atom is from 1 to about 20. The amount ofthe comonomer is from about 0.1% to about 99% by weight, desirably fromabout 1.5% to about 50% by weight, and preferably from about 2% to about10% by weight based upon the total weight of the one or more comonomersand the fluorooxetane monomers. A preferred copolymer is made fromtetrahydrofuran.

EXAMPLE CP (FOX-THF)

An example of preparing a poly-FOX-THF copolymer is as follows:

A 10 L jacketed reaction vessel with a condenser, thermocouple probe,and a mechanical stirrer was charged with anhydrous methylene chloride(2.8 L), and 1,4-butanediol (101.5 g, 1.13 moles). BF₃THF (47.96 g,0.343 moles) was then added, and the mixture was stirred for 10 minutes.A solution of 3-FOX, 3-(2,2,2-trifluoroethoxyl-methyl)-3-methyloxetane,made in accordance with U.S. Pat. Nos. 5,650,483; 5,668,250; 5,663,289;or 5,668,251, (3,896 g. 21.17 moles) in anhydrous methylene chloride(1.5 L) was then pumped into the vessel over 5 hours. The reactiontemperature was maintained between 38 and 42° C. throughout theaddition. The mixture was then stirred at reflux for an additional 2hours, after which ¹H NMR indicated >98% conversion. The reaction wasquenched with 10% aqueous sodium bicarbonate (1 L), and the organicphase was washed with 3% aq. HCl (4 L) and with water (4 L). The organicphase was dried over sodium sulfate, filtered, and stripped of solventunder reduced pressure to give 3,646 g (91.2%) of title glycol, a clearoil. NMR: The average degree of polymerization (DP) was determined byend group anaylsis. The hydroxl functional end groups were reacted withtrifluoroacetic anhydride at room temperature and the derivativecompound characterized by ¹H-NMR spectroscopy. The degree ofpolymerization was calculated by the ratio of the area of the methylresonance and the area of terminal methylene. The DP was 15.2 whichtranslates to an equivalent weight of 2804. The THF content of thisglycol, as determined by ¹H NMR, was 2.5% wt THF (6.2% mole THF). Thisexample was included to teach how to polymerize partially fluorinatedoxetane polymers.

Copolymer Formation

The above-noted fluorinated oxetane oligomers, polymers, or copolymerscan subsequently be reacted with another polymer and/or curing agent toform a copolymer or a cured polymer or a cured copolymer. Examples ofsuitable monomers forming a copolymer include the above noted monomerssuch as the various cyclic ethers, the various acrylic monomers, thevarious vinyl substituted aromatic monomers, the various polyesterforming monomers, the various polyurethane forming monomers, or thevarious polyamide forming monomers, or the various siloxane monomers,all of which are hereby fully incorporated by reference. The variouscuring or crosslinking agents are known to the literature and to the artand include the various amino resins as set forth herein below. Thesecopolymer forming monomers and/or curing agents are reacted with thewetting, or flow, or leveling agents subsequent to formation thereof.

Poly(Fluorooxetane-Ester) Copolymers

As noted above, copolymers of the polyoxetane with another monomer orpolymer can be made. Preparation of various polyoxetane-ester copolymersand desirable block copolymers are set forth in U.S. application Ser.No. 09/035,595, filed Mar. 5, 1998; Ser. No. 09/244,711, filed Feb. 4,1999; Ser. No. 09/384,464, filed Aug. 27, 1999; Ser. No. 09/698,554,filed Oct. 27, 2000, and Ser. No. 10/091,754 filed Mar. 6, 2002, whichare hereby fully incorporated by reference. A desired copolymer is thatof an oxetane and an ester. The polyester can be preformed and reactedwith the polyoxetane or formed in situ by reacting ester formingmonomers with the polyoxetane. However, it is highly desirable toprereact, endcap, the hydroxyl terminated fluorinated polyoxetanepolymer, or copolymer, (polyoxetane block) with a polycarboxylic acid oranhydride thereof for ease of incorporation of the fluorinated moietyinto a polyester via an ester linkage. This route increases the rate ofincorporation, and generally the percentage of fluorinated polyoxetanethat is incorporated into the polyester or other polymer. Subsequentthereto, the polyester block can be formed. Such block copolymers

can then be cured utilizing amino resins.

A preferred route to form the ester linkage is to react the hydroxylterminated partially fluorinated polyoxetane with at least 2 moles of acarboxylic acid from a polycarboxylic acid having from 3 to 10 or 30carbon atoms such as malonic acid, or succinic acid, or glutaric acid,or adipic acid, or pimelic acid, or maleic acid, or fumaric acid, orcyclohexane dioic acid, and the like, an anhydride, thereof, perequivalent of hydroxyl groups from any polyol component under conditionseffective to form an ester condensation product from the hydroxyl groupof the polyoxetane and the carboxylic acid group of the polycarboxylicacid or its anhydride. More desirably, the equivalents of carboxylicacid groups are at least 2.05 or 2.1 equivalents. The reactiontemperature is generally from about 110 to about 275° C. and desirablyfrom about 215° C. to about 250° C. In a preferred embodiment, theamount of non-fluorinated polyol is small or zero to force thecarboxylic acid groups to react with the hydroxyl group of the partiallyfluorinated polyoxetane. Desirably, the equivalents of hydroxyls fromnon-fluorinated polyols are less than 0.5, more desirably less than 0.2and preferably less than 0.1 per equivalent of hydroxyls from thepartially fluorinated polyoxetane until after at least 70, 80, 90, or 95mole percent of the hydroxyl groups of the polyoxetane are converted tohalf esters with the polycarboxylic acid. It is also acknowledged thatthe percentage of the polymer with said oxetane repeating units and theoxetane repeating units themselves may not be uniformly distributedthrough the bulk of the polyester. Said oxetane repeating units areusually disproportionately present at the surface of the coating due tothe low surface tension of those repeat units. The amount of surfacefluorine groups can be determined by XPS (x-ray photoelectronspectroscopy).

The polyester resins are made by a condensation polymerization reactionin the presence of heat and usually a catalyst with polycarboxylic acidsor anhydrides thereof and polyols. Alternatively, internal or cyclicesters can be utilized containing a total of from about 4 to about 15carbon atoms such as caprolactone. Reaction temperatures generally rangefrom about 110° C. to about 275° C., and desirably from about 215° C. toabout 250° C. with suitable catalysts being such compound as dibutyl tinoxide and the like. Reaction temperatures of the cyclic esters aregenerally lower, such as from about 10° C. or 20° C. to about 30° C. or50° C. or 100° C. Preferred polycarboxylic acids are the dicarboxylicacids and their anhydrides. Fatty monobasic oils or fatty acids,monohydroxy alcohols and anhydrides can be present. The polyester maycontain active hydrogen atoms, e.g., carboxylic acid groups and/orhydroxyl groups for reaction with the amino resin or can containunsaturation for crosslinking by another mechanism such ascopolymerization with ethylenically unsaturated monomers. Examples ofsome acids to use to form the alkyd resin or reactive polyester areadipic acid, cyclohexane dioic acid, azelaic acid, sebacic acid,terephthalic acid, isophthalic acid, phthalic anhydride, and so forth.Generally the aliphatic carboxylic acids have from about 3 to about 10carbon atoms. Other carboxylic acids such as carbonic acid or phosgenemay be used in lieu of carboxylic acids under appropriate conditions.The aromatic carboxylic acids generally have from about 8 or 10 to about25 or 30 carbon atoms. The polyhydric alcohols (polyols) generally havefrom about 2 to about 20 carbon atoms and from about 2 to about 5hydroxyl groups. Polymeric polyols such as formed from thepolymerization of cyclic alkylene oxides may be used as a portion or allof the polyhydric alcohol. Polymeric polyols generally have numberaverage molecular weights from 100 to 5,000 or 10,000. Examples of somepolyhydric alcohols include ethylene glycol, propylene glycol,diethylene glycol, dipropylene glycol, glycerine, butylene glycol,2,2-dimethyl-1,3-propanediol, trimethylol propane,1,4-cyclohexanedimethanol, pentaerythritol, trimethylolethane and thelike. Mixtures of the polyols and polycarboxylic acids can be used. Anexample of a suitable reactive polyester is the condensation product oftrimethylol propane, 2,2-dimethyl-1,3-propanediol,1,4-cyclohexanedimethanol, isophthalic acid or phthalic anhydride, andadipic acid, hereinafter “VR-248 resin”. Mixtures of these reactivepolyesters (alkyd resins) can be used. Alkyd resins are well known asshown by the “Encyclopedia of Polymer Science and Technology,” Vol. 1,1964, John Wiley & Sons, Inc., pages 663–734; “Alkyd Resins,” Martens,Reinhold Publishing Corporation, New York, 1961 and “Alkyd ResinTechnology,” Patton, Interscience Publishers, a division of John Wileyand Sons, New York, 1962. Some unsaturated polycarboxylic acids andunsaturated polyols may be used in the condensation reaction.

The polyester segments of the polyester may also be polymerized fromcyclic ethers typically containing 2 or 3 or 4 carbon atoms in the ringand an anhydride (e.g. an unsaturated anhydride) using double metalcomplex cyanide catalysts. These polyesters can be used with acarboxylic half ester functionalized polyoxetane because of theoccurrence of ester interchange reactions whereby polyester polymerscleave to form carboxylic acid and hydroxyl end groups and then couplewith other polyester fragments via an ester linkage. Generally anycyclic oxide can be utilized such as 1,2-epoxides, oxetanes, and thelike, with the cyclic ether having a total of up to 18 carbons atoms, asfor example 2 carbon atoms in the ring and up to 16 carbon atoms in theside chains. Such cyclic oxide monomers can also contain one or morealiphatic double bonds. Generally five-member unsaturated cyclicanhydrides are preferred, especially those having a molecular weightbetween 98 and 400. Mixed anhydrides can be used. Anhydrides includephthalic, itaconic, nadic etc. Halogenated anhydrides can also be used.Such polyesters are known to the art and described in U.S. Pat. No.3,538,043 which is hereby incorporated by reference.

The number average molecular weight of the polyester polymer or block,whether preformed, or formed in situ, is desirably from about 100 toabout 5,000 or 20,000. It is understood that in all these reactions, thepossibility exists that some of the polyester molecules will not includeany polyoxetane. The polyester compositions of the present invention canbe formed by reacting the ester forming monomers in the presence of aderivative of the above noted fluorinated polyoxetane polymer, orcopolymer which contains an ester linkage derived from the reaction of apolycarboxylic acid or anhydride with the fluorooxetane. Alternatively,a preformed polyester can be formed which is then reacted with thefluorinated polyoxetane polymer, or copolymer containing the noted esterlinkage. In other words, the polyester can be formed or derived orpolymerized in the presence of the polyfluorooxetane derivative or itcan be initially polymerized and subsequently reacted as through ahydroxyl end group with a polyoxetane having the ester linkage thereon.

The amount of fluorinated polyoxetanes in said polyester is desirablyfrom about 0.05 or 0.1 or 0.2 to about 10, 15 or 50 weight percent basedon the weight of the polyester including the polyoxetane portion. Thepolyester can be diluted with other components (includingnon-fluorinated polyesters) while preparing a coating or other polymercomposition. The repeating units from a polyester are desirably fromabout 50 to about 99.8 weight percent of the polyester and polyoxetaneand more desirably from about 85 or 90 to about 99 weight percent.

Additionally other conventional additives may be formulated into thepolyester-polyoxetane composition for particular applications. Examplesinclude viscosity modifiers, antioxidants, antiozonants, processingaids, pigments, fillers, ultraviolet light absorbers, adhesionpromoters, emulsifiers, dispersants, solvents, crosslinking agents, etc.

Since the poly(fluorooxetane-ester) copolymers described hereinabovegenerally contain a hydroxyl end group or can be formulated to readilycontain such an end group, they can be utilized with such a polar groupthereon. Alternatively, they can be reacted with various compounds toproduce an anionic, cationic, nonionic, or amphoteric end groups in amanner as set forth hereinabove, and hereby fully incorporated byreference. Such poly(fluorooxetane-ester) copolymers containing one ormore polar groups thereon, and often two polar groups, can be utilizedas wetting agents, or flow agents, or leveling agents for various usesas set forth herein below. The ester portion of thepoly(flurooxetane-ester) copolymers will generally act as acompatibilizing agent for the flurooxetane portion of the copolymer andimprove solubility as well as incorporation into various other polymers.Such copolymers can act as a non-fugitive wetting, or flow, or levelingagent.

Various polyfluorooxetane-polyester copolymers were made in thefollowing manner.

EXAMPLE CP-I

Two different hydroxyl terminated fluorinated polyoxetane-THF copolymerswere made in a manner as set forth in Example CP to prepare fourdifferent polyester materials. The first polyoxetane had 6 mole %repeating units from tetrahydrofuran (THF) with the rest of the polymerbeing initiator fragment and repeating units from 3-FOX where n=1, R_(f)is CF₃, and R is CH₃. The number average molecular weight of the firstpolyoxetane was 3400. The second polyoxetane had 26 mole % of itsrepeating units from tetrahydrofuran with the residual being theinitiator fragment and repeating units from 3-FOX. 3-FOX is also knownas 3-(2,2,2-trifluoroethoxylmethyl)-3-methyloxetane.

EXAMPLE CP-II Fox—Polyester Copolymers

The first and second fluorinated oxetane polymers of Example CP-I werereacted with at least a 2 equivalent excess (generally 2.05–2.10 excess)of adipic acid in a reactor at 455° F. for 3.5 hours to form apolyoxetane having the half ester of adipic acid as end groups. Thishalf ester linkage will serve to chemical bond the polyoxetane to asubsequently in-situ formed polyester. In other words, this polyoxetanehas a preformed ester linkage. NMR analysis was used to confirm thatsubstantially all the hydroxyl groups were converted to the estergroups. The average degree of polymerization of the first oxetanepolymer was reduced from 18 to 14 during the reaction with adipic acid.The average degree of polymerizations of the second oxetane polymerremained at 18 throughout the reaction. The reactants were then cooledto 300° F.

The adipic acid functionalized polyoxetane was then reacted withadditional diacids and diols to form polyester (VR-248) blocks. Thediacids were used in amounts of 24.2 parts by weight of adipic acid and24.5 parts by weight of isophthalic acid. The diols were used in amountsof 20.5 parts by weight cyclohexanedimethanol, 14.8 parts by weightneopentyl glycol, and 16.0 parts by weight trimethylol propane. Therelative amounts of the adipate ester of the oxetane polymer and thepolyester forming components was adjusted to result in polyesters witheither 2 or 4 weight percent of partially fluorinated oxetane repeatingunits. The reactants were reacted in the same pot used to react theadipic acid but the reaction temperature was lowered to 420° F. Thereaction time was continued until the calculated amount of water wasgenerated. The finished batch sizes were from 20 to 30 gallons.

EXAMPLE CP-III Fox—Caprolactone Copolymers

This example relates to the reaction of caprolactone monomers in thepresence of a fluorinated polyoxetane to generally form a blockfluorinated polyoxetane-ester copolymer. The copolymer can contain ahydroxyl end group. However, inasmuch as the copolymer contains alactone group, the same can be modified in a manner set forthhereinabove to contain other polar groups, for example an anion, or acation, or both, or a nonionic, thereby rendering the copolymer morewater soluble.

Preparation of a Oxetane Caprolactone (Ester) Copolymers

Mole d Compound Ratio MW Moles Ratio (g/mL) mL Scale 3-FOX 100.0 1.0184.15 0.54 50.34 1.150 87.0 Caprolactone 0.54 114.14 0.47 43.86 0.88660.9 Methylene Chloride 0.53 84.93 0.62 57.85 1.330 39.8 Neopentylglycol 0.02812 104.15 0.03 2.50 1.017 2.8 BF₃THF 0.015092 139.90 0.011.00 1.268 1.2 Methylene Chloride 0.8 84.93 0.94 87.32 1.330 60.2 Water0.43 18.01 2.39 221.32 1.000 43.0 Water 0.85 18.01 4.72 437.50 1.00085.0 Theoretical Yield (g) 156.81 Expected Yield, Low (g) 141.13Expected Yield, High (g) 148.97 Solids Loading, % 47.32 mL InitialVolume 191.71 Volume after quench, 294.86 ml Volume after wash, mL336.86

To a 250 mL 3-necked round bottomed flask was added neopentyl glycol(2.81 grams, 0.03 moles), 53 mL methylene chloride, and BF₃THF (1.51 g,0.01 moles). 3-FOX monomer (100 g, 0.54 moles) was added dropwise over40 minutes. After two hours, proton-NMR analysis indicatedpolymerization of the 3-FOX monomer was complete with a degree ofpolymerization of 19.14. Caprolactone monomer (54 grams, 0.47 moles) wasadded dropwise over 25 minutes. The reaction mixture was then allowed tostir for 120 hours at 25° C. 80 grams of methylene chloride was thenadded, and the copolymer solution was washed with water until a neutralpH was obtained. Final yield was 141.15 grams, the FOX—caprolactonedegree of polymerization was 15.85, and the hydroxyl equivalent weightwas 2717.4.

As noted above, the various fluorinated polar group containing polymersof the present invention act as a flow, or a leveling, or a wettingagent. Desirably they are incorporated or tied up, in other words boundto another polymer as in the form of a copolymer or the like to preventthe fluorinated polymer from being fugitive, able to leach out, orotherwise be released from a composition such as a coating compositionor any other composition wherein a plurality of compounds are contained.Other than being in the form of a copolymer, they can be cured aftereffectively serving as a flow, or leveling, or wetting agent and formedinto a final product such as a coating, a laminate wherein thefluorinated polymer is contained on a substrate, or other article. Thefollowing thus relates to a curing poly(fluorooxetane-ester) copolymerswhich can contain a polar group thereon.

Cured Poly(Fluorooxetane-Ester) Copolymers

As noted above, the polyoxetane-ester copolymer can be cured utilizingamino resins. Amino resins generally include alkylatedbenzoguanamine-formaldehyde, alkylated urea-formaldehyde, or preferablyalkylated melamine-formaldehyde resin where the alkyl group containsfrom 1 to 6 carbon atoms. Mixtures of these resins can be used. Theseamino resins are well known and include those set forth in“Aminoplastics,” Vale et al, Iliffe Books Ltd., London, 1964; “AminoResins,” Blair, Reinhold Publishing Corporation, New York, 1959, “ModernPlastics Encyclopedia 1980–1981,” pages 15, 16 and 25 and “Encyclopediaof Polymer Science And Technology,” John Wiley & Sons, Inc., Vol. 2,1965, pages 1 to 94.

These materials are desirably cured at temperatures of at least 150° F.,200° F., 250° F. or 400° F. or more (66° C., 93° C., 121° C., or 204°C.) for effective times in the presence of a minor amount by weight ofan acidic catalyst such as boric acid, phosphoric acid, acid sulfates,hydrochlorides, phthalic anhydride or acid, oxalic acid or its ammoniumsalts, sodium or barium ethyl sulfates, aliphatic or aromatic sulfonicacids such as p-toluene sulfonic acid (preferred), methane sulfonic acidand the like. It is important that properties such as stain resistanceimparted by the polyester and amino resin containing repeat unitsderived from an oxetane monomer having pendant fluorinated groups beoptimized by controlling things such as glass transition temperature,crosslink density and the presence of molecules that may act asplasticizers or other molecules that may transport or attract stainingmolecules in the coating. Prior to curing flattening agents or otheradditives can be added to the mixture of the reactive polyester andamino resin.

The amount of the various components in the coating will be generallyspecified in relationship to 100 parts by weight of thepolyester-oxetane resin and the amino resin crosslinking agent. Theweight ratio of polyester-oxetane resin (neat) to amino resin (neat) canvary widely but desirably is from about 10:90 to 90:10 and moredesirably from about 20:80 to 80:20; or 70:30 to 30:70, or 60:40 to40:60. Generally, it is more desirable to match the moles of reactivegroups on the polyester-oxetane to within 10% to 20% to the number ofmoles of reactive groups on the amino resin. The number of moles ofreactive groups can be determined by dividing the weight of thecomponent by the equivalent weight for the component. The term “neat”after polyester-oxetane and amino resin does not exclude usingpolyesters and amino resins that are received dissolved in solvents ordispersed in water but rather specifies that the amount used is to berecalculated based on the weight without the solvent. For the purposesof this disclosure no distinction will be made whether the amino resincrosslinks the polyester resin or vice versa.

The amount of carriers and/or solvent(s) in the coating composition canvary widely depending on the coating viscosity desired for applicationpurposes, and solubility of the components in the solvent. Thesolvent(s) can be any conventional solvent for polyester-amino resinsystems. These carriers and/or solvents include but are not limited towater, alkyl alcohols of 1 to 10 carbon atoms, ketones of from 3 to 15carbon atoms e.g. methyl ethyl ketone or methyl isobutyl ketone,alkylene glycols and/or alkylene glycol alkyl ethers having from 3 to 20carbon atoms, acetates and their derivatives, ethylene carbonate, etc.Illustrative U.S. patents of the carrier and/or solvent systemsavailable include U.S. Pat. Nos. 4,603,074; 4,478,907; 4,888,381 and5,374,691 hereby incorporated by reference for their teachings both ofcarriers and/or solvent systems and of polyesters and amino resins.While most acetate type solvents can be used, e.g. n-butyl acetate, apreferred solvent is n-propyl acetate. The amount of solvent(s) candesirably vary from about 20 parts by weight to about 400 parts byweight per 100 parts by weight of total polyester resin and amino resin.

The amount of catalyst is an amount that effectively catalyzes themutual crosslinking of the polyester and amino resins under thecrosslinking conditions chosen (usually elevated temperatures). As thecrosslinking temperature increases above 150° F., 200° F., 250° F. or400° F. (66° C., 93° C., 121° C. or 204° C.) the amount of can bereduced. Effective amounts of catalyst can vary from about 0.1, 0.5 or 1to about 6 or 8 parts by weight and preferably from about 2 or 3 toabout 6 parts by weight per 100 parts by weight total of said polyesterand amino resins.

The poly(oxetane-THF-ester) of Example CP II was cured in a manner asfollows.

EXAMPLE CP-IV

The four polyesters (2 or 4 wt. % oxetane and 6 or 26 mole percent ofthe polyoxetane being repeating units from THF of Example CP-II) wereformulated into solvent based coating compositions as shown in Table 1.The Resimene 747 resin is an amino resin curative(alkylmelamine-formaldehyde) for polyester resins. The PTSA isparatoluene sulfonic acid catalyst (40 wt. % active in isopropanol). Thecoating compositions varied in the amount of polyoxetane in thepolyester, the amount of tetrahydrofuran repeating units in thepolyoxetane, and the weight ratio of Resimene to polyester. The coatingcompositions were applied to plasticized polyvinyl chloride substrate ina conventional manner without any intermediate tie coat. The coatingswere cured by heating to approximately 240° F. (116° C.) for about oneminute.

TABLE I Components Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 n-propylacetate 8.3 8.3 8.3 8.3 8.5 THF 0.925 10.9 10.9 10.9 10.9 Polyesterhaving 2 wt. % of 18.95 0 0 0 16.8 1st oxetane (6 mol % THF) Polyesterhaving 4 wt. % of 0 0 0 18.95 0 1st oxetane(6 mol % THF) Polyesterhaving 2 wt. % 2^(nd) 0 18.95 0 0 0 oxetane(26 mol % THF) Polyesterhaving 4 wt. % 2^(nd) 0 0 18.95 0 0 oxetane(26 mol % THF) Resimene 74718.55 18.55 18.55 18.55 20.15 PTSA 3.3125 3.3125 3.3125 3.3125 3.6n-propyl acetate 8.5 8.5 8.5 8.75 8.75 THF 10.9 10.9 10.9 11.0 11.0Polyester having 2 wt. % 0 0 0 0 0 1st oxetane(6 mol % THF) Polyesterhaving 4 wt. % 0 0 16.8 14.6 0 1st oxetane (6 mol % THF) Polyesterhaving 2 wt. % 16.8 0 0 0 0 2^(nd) oxetane(26 mol % THF) Polyesterhaving 4 wt. % 0 16.8 0 0 14.6 2^(nd) oxetane(26 mol % THF) Resimene 74720.15 20.15 20.15 21.75 21.75 PTSA 3.6 3.6 3.6 3.9 3.9 The units in thetable above are grams.

It should be noted that the recipe set forth in Table 1 results in highamounts of fluorine on the surface of the coating and the high amountsof fluorine are associated with low surface energy, good abrasionresistance, and easy cleaning. Good results were also obtained withrespect to wetting, or flow, or leveling. Similar or identical recipeshave resulted in 15–18 atomic percent fluorine on the surface asdetermined by XPS. This is generally a 30–50 percent increase oversimilar recipes using similar amounts of partially fluorinatedpolyoxetane but without pre-reaction of the polyoxetane into thepolyester, e.g. the following control.

All example coatings CP-IV-2 through CP-IV-7 were prepared in the samefashion:

The components of the coating are allowed to mix for approximately twominutes. Typically, the coating is applied with a RDS 10 wire-bound rodto a white vinyl substrate. A majority of the solvent is removed quicklyusing a heat lamp (˜150° F.). The coating is cured by heating to 250° F.for three minutes. Poly(3-FOX-ester) is (Poly-3-FOX modified polyester)as described above.

EXAMPLE CP-IV-2

Effect of Poly-3-FOX diol addition on wetting, flow and leveling onpolyester/melamine coatings of various solids levels

VR-248 Resimene i-Propyl Poly-3- % Resin Sample Resin 747 PTSA AcetateFOX diol^(†) Solids A 5.00 1.72 0.16 4.74 — 45.0 B 5.00 1.72 0.16 3.44 —50.0 C 5.00 1.72 0.16 1.48 — 60.0 D 5.00 1.72 0.16 0.09 — 70.0 E 5.001.72 0.16 4.74 0.015 45.0 F 5.00 1.72 0.16 3.44 0.015 50.0 G 5.00 1.720.16 1.48 0.015 60.0 H 5.00 1.72 0.16 0.09 0.015 70.0 Composition givenin grams. ^(†)Average DP = 18.5; R_(f) = CH₂CF₃.

Sample Coating Appearance 60° Gloss A Good 66.9 ± 1.2 B Good coating butmany bubbles in bulk of 33.2 ± 2.5 coating C Complete dewetting ofcoating from — substrate D Complete dewetting of coating from —substrate E Good 86.6 ± 1.7 F Good 92.0 ± 0.6 G Good 97.8 ± 0.8 H Goodbut small pinholes present on surface 94.2 ± 1.4Addition of Poly-3-FOX diol able to wet, flow and level at a variety ofwt % solids.

EXAMPLE CP-IV-3

Effect of Poly-3-FOX diol additive amount on wetting, flow and levelingon polyester/melamine coatings at 70 wt % solids.

VR-248 Resimene n-Propyl Poly-3- Sample Resin 747 PTSA acetate FOXdiol^(a) A 2.83 3.34 0.19 0.20 — B 2.83 3.34 0.19 0.20 0.0068 C 2.833.34 0.19 0.20 0.0229 D 2.83 3.34 0.19 0.20 0.0532 Composition given ingrams. ^(a)Average DP = 18; R_(f) = CH₂CF₃. Sample Coating appearance AComplete dewetting of coating from substrate B Good coating C Goodcoating D Good coating Even small levels of Poly-3-FOX diol provide forgood wetting, flow and leveling.

EXAMPLE CP-IV-4

Effect of average degree of polymerization of Poly-3-FOX additives onwetting, flow and leveling of a polyester/melamine coating at 70 wt %solids.

VR-248 Resimene n-Propyl Poly-3- Sample Resin 747 PTSA acetate FOX diolA 2.83 3.34 0.19 0.20 — B 2.83 3.34 0.19 0.20 0.0075^(a) C 2.83 3.340.19 0.20 0.0068^(b) D 2.83 3.34 0.19 0.20 0.0078^(c) Composition givenin grams. ^(a)Average DP = 6.7. ^(b)Average DP = 18. ^(c)Average DP =23. Gloss Sample Coating appearance 20° 60° A Complete dewetting ofcoating from — — substrate B Complete dewetting of coating from — —substrate C Good coating 47.3 ± 1.3 86.6 ± 14  D Good coating 55.7 ± 3.997.3 ± 0.4

EXAMPLE CP-IV-5

Effect of R_(f) length of PolyFOX additive on wetting, flow and levelingproperties of polyester/melamine coating at 70 wt % solids.

VR-248 Resimene n-Propyl PolyFOX Sample Resin 747 PTSA acetate diol A2.83 3.34 0.19 0.20 — B 2.83 3.34 0.19 0.20 0.015^(a) C 2.83 3.34 0.190.20 0.015^(b) D 2.83 3.34 0.19 0.20 0.016^(c) Composition given ingrams. ^(a)Poly-3-FOX; average DP = 35; R_(f) = CH₂CF₃. ^(b)Poly-5-FOX;average DP = 5.4; R_(f) = CH₂CF₂CF₃. ^(c)Poly-7-FOX; average DP = 9.8;R_(f) = CH₂CF₂CF₂CF₃. Sample Coating appearance 60° Gloss A Completedewetting of — coating from substrate B Good coating 102.2 ± 1.3 C Goodcoating 101.4 ± 0.9 D Good coating 100.9 ± 1.7 Short R_(f) chainmaterials effective wetting, flow and leveling agents.

EXAMPLE CP-IV-6A

Comparison of Poly-3-FOX diol additives and commercially availablefluorosurfactant wetting, flow and leveling agents in polyester/melaminecoatings at 70 wt %.

VR- n- Sam- 248 Resimene Propyl ple Resin 747 PTSA acetate AdditiveAmount A 2.83 3.34 0.19 0.20 — — B 2.83 3.34 0.19 0.20 Poly-3-FOXdiol^(a) 0.015 C 2.83 3.34 0.19 0.20 ZONYL FSO^(b) 0.015 D 2.83 3.340.19 0.20 ZONYL FS-300^(c) 0.015 E 2.83 3.37 0.19 0.20 FluoroadFC-430^(d) 0.015 Composition given in grams. ^(a)Average DP = 18, R_(f)= CH₂CF₃. ^(b)From DuPont; F(CF₂)_(~8)CH₂CH₂O(CH₂CH₂O)_(x)H. ^(c)FromDuPont; F(CF2)_(~8)CH₂CH₂O(CH₂CH₂O)_(z)H. ^(d)From 3M; Fluoroaliphaticpolymeric esters. Gloss Sample Coating appearance 20° 60° A Completedewetting of coating from — — substrate B Good coating 69.4 ± 2.2 101.0± 1.1 C Complete dewetting of coating from — — substrate D Completedewetting of coating from — — substrate E Partial dewetting of coatingfrom — — substratePolyFOX materials more effective wetting, flow and leveling agents inthis particular system compared to commercially availablefluorosurfactants sold as wetting, flow and leveling agents.

Another comparison of Poly-3-FOX diol-copolymer as a flow, wetting, orleveling agent is set forth herein below. The coating is a solvent basednitrocellulose on leneta charts

EXAMPLE CP-IV-6B

Compound Coating Comments 3M Nonionic fluorosurfactants FC-430 (1000ppm) inferior leveling, small bubbles FC-430 (2500 ppm) defects incoating FC-430 (5000 ppm) small bubbles FC-430 (7500 ppm) nice coatingDuPont nonionic fluorosurfactant ZONYL FSO (1000 ppm) coatingcontraction, insufficient wetting ZONYL FSO (2500 ppm) coatingcontraction, insufficient wetting ZONYL FSO (5000 ppm) nice coatingZONYL FSO (7500 ppm) nice coating, glossy Poly-3-Fox-Co-THF Poly Fox T-40% (1000 ppm) insufficient wetting Poly Fox T- 40% (2500 ppm) Excellentcoating Poly Fox T- 40% (5000 ppm) Excellent coating Poly Fox T- 40%(7500 ppm) Excellent coating

As apparent from the above, a block copolymer of the present inventiongave good results and low cratering as compared to the 3M or DuPontmaterial.

EXAMPLE CP-IV-7

Effect of Poly-3-FOX modified polyester on wetting, flow and leveling ofa polyester/melamine coating at various solids levels

Polyester of CP IV - VR- Table 1 - 248 Resimene n-Propyl Wt % Sampleline 3 Resin 747 PTSA acetate Solids A 2.83 3.34 0.19 0.20 70.0 B 2.83 —3.34 0.19 6.41 40.0 C 2.83 — 3.34 0.19 0.20 70.0 Composition given ingrams. Sample Coating appearance A Complete dewetting of coating fromsubstrate B Good coating C Good coatingA PolyFOX modified polymer is effective also as an in-situ wetting, flowand leveling agent that is then made non-fugitive by crosslinking orreacting into the coating.

As apparent from Examples CP-IV-2 through CP-IV-7, Poly-3-FOX diol perse

is a good flow, wetting and leveling agent for apolyester-melamine-formaldehyde

system.

EXAMPLE CP-V

Another example of a fluorinated polymer of the present invention is afluorinated methacrylate. A specific example of such a polymer istrifluoroethyl methacrylate-butyl acrylate copolymer (75/25 mole %)obtained by free radical copolymerization of trifluoroethyl methacrylate(Aldrich Chemical Co.) and butyl acrylate (Aldrich Chemical Co.) intoluene at 60–65° C. using AIBN as initiator. This copolymer has a cyanopolar group thereon, incorporated from an initiator fragment.

The various ingredients in Table II were allowed to mix forapproximately two minutes. Typically, the coating is applied with a RDS10 wire-bound rod to a white vinyl substrate. A majority of the solventis removed quickly using a heat lamp (˜150° F.). The coating is cured byheating to 250° F. for three minutes.

TABLE II n-Propyl TFEMA/BA VR-248 Resimene p-Toluene AcetateCopolymer^(‡) Sample^(†) Resin (g) 747 (g) Sulfonate (g) (g) (g) A 2.833.34 0.19 0.20 — B 2.83 3.34 0.19 0.20 0.0337 (0.1 wt %) C 2.83 3.340.19 0.20 0.0843 0.25 wt % D 2.83 3.34 0.19 0.20 0.1693 (0.50 wt %) E2.83 3.34 0.19 0.20 0.3403 (1.0 wt %) Sample Coating Appearance AComplete dewetting B Partial dewetting; large amounts of orange peel CPartial dewetting; large amounts of orange peel D Partial dewetting;large amounts of orange peel E Good coating ^(†)All formulations are 70wt % solids. ^(‡)Trifluoroethyl methacrylate/butyl acrylate copolymer.Mn ≈ 5,000 g/mol.

Generally, when a fluorinated polyacrylic is utilized, the amountthereof to achieve a suitable wetting, flow, or leveling effect isgenerally from about 0.05 wt % to about 5 wt % and desirably from about0.75 wt % to about 3 wt % based upon the total weight of the fluorinatedacrylate polymer or copolymer, the amino curing resin, and the polyesterresin.

Monohydroxylfluorooxetanes

Instead of an oxetane polymer having two hydroxyl end groups as informulas 3A and 3B, a fluorine containing polymer having only oneterminal hydroxyl group can be utilized. Such polymers are made byutilizing a mono alcohol initiator. A more detailed description of thepreparation of the monofluorooxetanes is set forth in U.S. Ser. No.09/473,518, filed Dec. 28, 1999 and Ser. No. 09/727,637, filed Dec. 1,2000, which are hereby fully incorporated by reference.

Generally, any type of monoalcohol can be utilized to produce themonohydroxyl polyfluorooxetane (MOX) polymer, or copolymer compositionof the present invention. Suitable monoalcohols generally includeorganic alcohols having from 1 to about 40 and preferably from about 1to about 18 carbon atoms; polymeric alcohols; or tetrafluoroethylenebased telomer alcohols. Examples of specific types of monohydric organicalcohols include the various aliphatic, aromatic, etc. alcohols such asalkyl alcohols, for example methyl alcohol, ethyl alcohol, propylalcohol, etc., or the olefinic alcohols, for example allyl alcohol, etc.or the alicyclic alcohols, for example, cyclohexanol, etc. or theheterocyclic alcohols, for example furfuryl alcohol, etc. Variousaromatic alcohols include benzyl alcohol, and the like. Moreover,halogenated organic alcohols and especially fluoroalcohols having from 2to 18 carbon atoms are desired such as trifluoroethanol,heptafluorobutanol, heptadecylfluorooctanol, and the like. Especiallypreferred monohydric alcohols include benzyl alcohol, trifluoroethanol,heptafluorobutanol, pentafluoropropanol, pentafluorobutanol,nonafluorohexanol, and other various perfluoroalkylethanols such aspentafluorobutanol, and allyl alcohol.

The polymeric alcohols are generally made from alkylene oxides havingfrom 2 to 6 carbon atoms with 2 or 3 carbon atoms, that is ethyleneoxide, propylene oxide, or tetrahydrofuran, or copolymers thereof beingpreferred. The number of repeat units of the polymeric alcohols cangenerally range from about 2 to about 50, desirably from about 3 toabout 30 with from about 5 to 20 repeat units being preferred.

Another group of monoalcohols are the various tetrafluoroethylene basedtelomer fluoroalcohols such as those commercially available from Dupontas Zonyl, from Clarion as Fluowet, from Elf-Atochem as Foralkyl 6HN, andthe like. Such fluoroalcohols have the general formulaCF₃CF₂(CF₂CF₂)_(x)CH₂CH₂OH where x is generally an integer of from 1 toabout 19 and preferably from about 8 to about 12. While some of thefluoroalcohols are crystalline or solid at room temperature all aremelted at temperatures of about 40° C.

While a monohydric alcohol can be utilized as an initiator incombination with a solvent, it is a preferred embodiment of the presentinvention to utilize a monohydric alcohol which serves as both aninitiator as well as a solvent for the fluorooxetane monomers and thelike. In other words, it is preferred that a solvent not be utilizedother than a monoalcohol which can also function as a solvent in that itsolubilizes the below noted oxetane monomers. Such co-initiator-solventalcohols are desired inasmuch as they produce linear low molecularweight polyfluorooxetane oligomers, polymers, or copolymers and mostpreferably oligomeric dimers, trimers, and tetramers having low cycliccontent. Such co-initiator-solvents include generally any of the abovenoted monoalcohols which solubilize the oxetane monomers with preferredalcohols including trifluoroethanol, benzyl alcohol, allyl alcohol,heptafluorbutanol, pentafluoropropanol, pentafluorobutanol,nonafluorohexanol, various perfluoroalkylethanols, and the like. The useof such co-initiator-solvent monoalcohols generally produces linearoligomers having less than about 10%, desirably less than about 8%, andpreferably less than about 5%, or 3%, or 2%, or less than about 1% byweight of cyclic oligomers based upon the total weight of generally theoligomers, and also any polymers, or copolymers if the same are alsoproduced. Similarly, if a polymer is produced, desirably the amount ofcyclic oligomer produced is low, i.e. the same values as set forthimmediately above, based upon the total weight of the polymers, and anyoligomers, or copolymers produced. In the same manner, if copolymers areproduced, the amount of cyclic oligomers is low based upon the totalweight of the copolymer, and any oligomer or polymer which also may beinherently produced.

Although solvents are preferably not utilized in order to produceoligomers, polymers or copolymers having low cyclic oligomer content, itis to be understood that low amounts of non-initiator solvents might beutilized such as generally less than 25% or 15% and preferably less than10%, 5%, 3% or nil by weight based upon the total weight of the smallamount of non-initiator solvent utilized and the monoalcohol.

As noted above, the oxetane monomer used to form the polyfluorooxetanehas the structure

where R, R_(f), and n are as set forth herein above.

The preparation of such fluorinated oxetane monomers was set forthherein above.

Generally any suitable cationic catalyst can be utilized to polymerizethe fluorooxetane monomers such as various Lewis acids and complexesthereof. Examples of such Lewis acid catalysts include Sn(IV)Cl₄,antimony pentafluoride, phosphorous pentafluoride, and the like, with acomplex of borontrifluoride and tetrahydrofuran being preferred.

According to a preferred embodiment of the present invention, amonoalcohol as hereinabove described is utilized as both an initiatorand solvent, i.e., no solvent or a very small amount of a solvent suchas dichloroethane is utilized. This preferred route will yield apolyfluorooxetane oligomer such as a homooligomer having an average DPof from about 2 to about 20, desirably from about 2 to about 10, andpreferably from about 2 to about 4 with very little cyclic oligomercontent as noted above. Such low molecular weight oligomers, e.g. dimersor trimers, are preferred inasmuch as when they are blended or reactedwith a coating formulation, they tend to migrate faster to the surfaceof the blend or coating and give lower surface tensions and thus resultin lower coefficient of friction as compared to polyfluorooxetaneshaving a higher average degree of polymerization. While not preferred,polyfluorooxetane polymers or of up to about 50, 100, or 150 can beutilized. Alternatively, but not preferably, copolymers can also bemade.

While not preferred, the polymerization can be carried out in thepresence of a Lewis acid catalyst and a Bronsted acid catalyst, as wellas a non-initiator or solvent for the fluorooxetane monomer. Examples ofsuitable non-initiator or non-monoalcohol solvents includetrifluorotoluene, dichloroethane, dimethylformamide, as well asdichloromethane. The amount of the alcohol initiator and catalyst foreither the above preferred or non-preferred embodiment will generallyvary inversely with the desired molecular weight of the polymer. Thatis, the polymerization is initiated by each alcohol and catalystmolecule generally on a quantitative basis for a given amount offluorooxetane monomer, hence, the molecular weight of thepolyfluorooxetane oligomer or polymer or copolymer will be determined bythe amount of alcohol utilized. When this route is utilized, the averagedegree of polymerization (DP) is also from about 2 to about 20,desirably from about 2 to about 10, and preferably from about 2 to about4, however, the degree of polymerization can also be up to 50, up toabout 100, or even up to about 150.

The reaction rate for forming the polyfluorooxetane oligomer, polymer,or copolymer, utilizing a monoalcohol and a Lewis acid catalyst willvary with temperature. Accordingly, the reaction time is generally from2 hours to 40 hours, and desirably is from about 4 to about 24 hours.The polymerization temperatures are generally from about 0° C. up toabout 100° C., and desirably from about 18° C. to about 50° C. Lowerreaction temperatures result in very slow reaction rates, whereas higherreaction temperatures will generally result in the formation of cyclicstructures containing from 3 to 4 oxetane units. As noted, monomerconversion to polymer is essentially quantitative. The monohydroxylpolyfluorooxetane oligomers, polymers or copolymers produced are washedwith water to obtain a neutral pH and the water removed as by decanting.Subsequently, any suitable desiccant can be utilized such as calciumchloride, phosphorus pentoxide, calcium carbonate, magnesium sulfate,molecular sieves, to dry the oligomers or polymers.

The monofunctional polyfluorooxetane oligomers or polymers generallyhave repeat units as set forth in formulas 3A and 3B above, and thepolymer formula is as follows:

where n, R, R_(f) and DP are described herein above and wherein R² isthe organic group of the reactive monoalcohol. That is, R² is derivedfrom an alcohol as noted above such as an organic alcohol having from 1to about 40 and preferably from 1 to about 18 carbon atoms, or apolymeric alcohol, etc. If more than one type of monoalcohol is utilizedto prepare the polyfluorooxetane oligomers or polymers, naturally the R¹of one or more different polymers, copolymers, or oligomers will bedifferent.

The fluorooxetane monomers, as noted above but not preferred, can becopolymerized with a variety of comonomers having epoxy (oxirane)functionality such as epichlorohydrin, propylene oxide, ethylene oxide,butyl glycidylether, and perfluorooctyl propylene oxide as well as alkylsubstituted oxiranes having from 1 to about 20 or from about 7 to about12 carbon atoms or mixtures thereof; monomers having a 4-membered cyclicether group such as trimethylene oxide, 3,3-bis(chloromethyl)oxetane,3,3-bis(bromomethyl)oxetane, and, 3,3-bromomethyl(methyl)oxetane;monomers having a 5 membered cyclic ether group such as tetrahydrofuran,tetrahydropyran, and 2-methyltetrahydrofuran; and the like. Still othersuitable monomers include 1,4-dioxane, 1,3-dioxane and 1,3-dioxalane aswell as trioxane and caprolactone. The copolymerization reaction iscarried out generally under the same conditions as is the polymerizationof the fluorooxetane monomers set forth hereinabove. The amount of thecomonomer is from about 0.1% to about 99% by weight, desirably fromabout 1.5% to about 50% by weight, and preferably from about 2% to about10% by weight based upon the total weight of the one or more comonomersand the fluorooxetane monomers.

Experimental

EXAMPLE MOX 1 Preparation of Monohydric Polyfluorooxetane Using BenzylAlcohol Initiator and Dichloromethane Solvent

Only glass reactors and condensers were used in this procedure. Allglassware and chemicals were dried prior to use. A 10 liter roundbottomed flask equipped with a condenser, addition funnel, and rubberseptum was charged with 1,763.4 grams of dichoromethane solvent. Thecatalyst, boron trifluoride-tetrahydrofuran (67.15 grams), and theinitiator benzyl alcohol, 129.7 grams, (mono-functional alcohol) wereadded to the reaction flask. 3-FOX (3,314.7 grams) were added to anaddition funnel. 3-FOX monomer can be made in a manner as set forth inU.S. Pat. Nos. 5,650,483; 5,668,250; 5,668,251; or 5,663,289.Approximately one-third of the mixture was added to the round-bottomedflask and allowed to stir for approximately 15 to 30 minutes until thereaction was initiated. The temperature was maintained at a temperatureof about 20 to 23° C. The remaining monomer mixture was added dropwiseover a four-hour period. The reaction mixture was allowed to stir fourhours until the conversion reached 97 to 99.8 percent as measured byH¹-NMR. The reaction mixture was washed with water to a neutral pH, thewater was decanted and the product was dried over magnesium sulfate. Theremaining solvents were removed at reduced pressure. The weight of thecyclic oligomers formed based upon the total weight of the copolymer wasapproximately 15% by weight.

EXAMPLE MOX 2 Preparation of Monohydric Polyfluorooxetane UsingTrifluoroethanol Initiator and Dichloromethane Solvent

Dichloromethane solvent (26.6 g) was introduced into a dry flask under adry nitrogen purge. BF₃-THF (7.57 g) catalyst was then slowly syringedinto the flask and the mixture stirred. While stirring, trifluoroethanol(initiator) (13.6 g) was slowly syringed into the reactor. The mixturetemperature was then brought to 35° C. and allowed to react forapproximately 30 minutes. Fifty grams (50 g) of 3-FOX monomer were thenslowly added to the reactor with good stirring and the temperature ofmixture monitored. A sample to determine monomer conversion by 1 H-NMRspectroscopy was taken shortly after a reaction exotherm is observed.Monomer addition continues at a rate to maintain a reaction temperaturebetween 38 and 40° C. After the monomer addition was complete, thereaction temperature was maintained in the range stated above for about2 hours, until quantitative conversion (>99.5 mole %) of the monomer wasachieved.

The polyether was isolated by diluting the mixture to a total of 1 mL ofdichloromethane per gram of 3-FOX monomer. The reactor contents are thentransferred to a suitably sized separatory funnel and the solutionquenched with 0.43 mL of water per gram of 3-FOX and vigorously shaken.After separation of the phases has occurred, the aqueous layer wasremoved, tested for pH and discarded. Water (0.85 mL/g 3-FOX) was againadded to the funnel and shaken vigorously together with the organiclayer. The phases were allowed to separate, the aqueous phase is againtested for pH and discarded.

This process was repeated until the pH of the aqueous phase was at least5. The organic phase was then subjected to rotating evaporation untilall the dichloromethane is gone as measured by NMR. Characterization byproton NMR spectroscopy showed the polyol to have an average degree ofpolymerization (DP) of 7.6 and a tetrahydrofuran (THF) comonomer contentof 14.3 mole %. The weight of the cyclic oligomers formed based upon thetotal weight of the copolymer was approximately 15% by weight.

EXAMPLE MOX 3 Preparation of Monohydric Polyfluorooxetane Using AllylAlcohol Initiator and Dichloromethane Solvent

Dichloromethane solvent (26.6 g) was introduced into a dry flask under adry nitrogen purge. BF₃-THF (2.53 g) was then slowly syringed into theflask and the mixture stirred. While stirring, allyl alcohol (initiator)(2.62 g) was slowly syringed into the reactor. The mixture temperaturewas then brought to 35° C. and allowed to react for approximately 30minutes. Fifty grams (50 g) of 3-FOX monomers were then slowly added tothe reactor with good stirring and the temperature of mixture monitored.A sample to determine monomer conversion by 1 H-NMR spectroscopy wastaken shortly after a reaction exotherm is observed. Monomer additioncontinues at a rate to maintain a reaction temperature between 38 and40° C. After the monomer addition is complete, the reaction temperaturewas maintained in the range stated above for about 2 hours, untilquantitative conversion (>99.5 mole %) of the monomer was achieved.

The polyether was isolated by diluting the mixture to a total of 1 mL ofdichloromethane per gram of 3-FOX monomer. The reactor contents are thentransferred to a suitably sized separatory funnel and the solutionquenched with 0.43 mL of water per gram of 3-FOX and vigorously shaken.After separation of the phases has occurred, the aqueous layer wasremoved, tested for pH and discarded. Water (0.85 mL/g 3-FOX) was againadded to the funnel and shaken vigorously together with the organiclayer. The phases were allowed to separate, the aqueous phase was againtested for pH and discarded. This process was repeated until the pH ofthe aqueous phase was at least 5. The organic phase was then subjectedto rotating evaporation until all the dichloromethane was gone asmeasured by NMR. Characterization by proton NMR spectroscopy showed thepolyol to have an average degree of polymerization (DP) of 8.3 and atetrahydrofuran (THF) comonomer content of 4.5 mole %. The weight of thecyclic oligomers formed based upon the total weight of the copolymer wasapproximately 15% by weight.

Examples 4, 5, and 6 relate to the preparation of monohydricpolyfluorooxetane copolymers using the same monoalcohol initiator as aco-initiator solvent and thus no non-monoalcohol solvent was utilized.

EXAMPLE MOX 4 Synthesizing Low MW 3-MOX Oligomer Using Trifluoroethanolas Co-Initiator-Solvent

Mole d g FW Moles Ratio g g/mL mL actual 3-FOX Monomer 184.15 0.272 5.0150.00 1.15 43.48 58.38 CF₃CH₂OH 100.04 0.136 2.5 13.6 1.373 9.91 9.91BF₃THF 139.91 0.054 1.0 7.6 1.268 5.99 7.6 CF₃CH₂OH 100.04 0.375 6.969.0 1.15 60 69 (Schent) Apparent DP = 3.6 (FOX) by end group analysisActually a mixture of linear dimer, trimer: tetramer A small amount ofcyclics 13.8 mole % THF, Theoretical = 14.6 mole %

By using trifluoroethanol as the initiator and solvent, very low MWlinear oligomers may be formed in high yields without the production ofsignificant amounts of cyclic oligomer. That is, the amount of cyclicoligomer formed was less than 1% by weight based upon the totalpolyfluorooxetane formed.

With regard to the preparation of Examples MOX 4, 5 and 6, all glasswareand reagents were dry prior to use. Water content of the reagents to beless than 500 ppm and confirmed by Karl Fisher analysis. Thetrifluoroethanol for initiation and BF3/THF were introduced into the dryflask under a dry nitrogen purge and allowed to stir for 30 mins. atroom temperature. The reaction flask was then heated to 40° C. and theremaining trifluoroethanol and 3-FOX solution were pumped into thereactor using the pump rate to keep the temperature below 54° C. Afterthe monomer addition was complete, the reaction temperature wasmaintained at 40° C. overnight. The polymer was isolated by diluting themixture with solvent and washing it with 5% sodium bicarbonate solutionand water until neutral. Dilution was to 1 g polymer to 1 mL of solvent.The makeup solvent was dichloromethane. The organic phase was thenseparated from the aqueous phase and subjected to rotating evaporationuntil all of the solvents had been removed. Characterization by protonNMR spectroscopy showed the polyol to have an average degree ofpolymerization (DP) of 3.6 by end group analysis.

EXAMPLE MOX 5 Synthesizing Low MW 3-MOX Oligomer Using Trifluoroethanolas Co-Initiator-Solvents

d A Substance Ratio MW Eq mmoles g/mL mL Used 3-FOX 0.741 184.15 2.0271.52 1.15 50.019 Monomer Trifluoro- 100.04 5.07 689.72 1.185 58.269.011 ethanol, co-initiator solvent Trifluoro- 0.0232 100.04 1.00136.00 1.00 13.6 13.611 ethanol, co-initiator solvent BF₃THF, 0.0125139.9 0.40 54.40 1.1 6.9 7.664 catalyst

The oligomer was prepared and purified in a manner as set forth inExample 4.

The average degree of polymerization was about 2 and the amount ofcyclic oligomer was less than 1% by weight based upon the total weightof polyfluorooxetane.

EXAMPLE MOX 6 Synthesizing Low MW 5-MOX Oligomer Using Trifluoroethanolas Co-Initiator-Solvents

d B Substance Ratio MW Eq mmoles g/mL mL used 5-FOX 0.741 234.15 1.8213.54 1.15 50.030 Monomer Trifluoro- 100.04 5.96 689.72 1.185 58.269.360 ethanol, co-initiator solvent Trifluoro- 0.0232 100.04 1.00115.77 1.00 11.6 11.625 ethanol, co-initiator solvent BF₃THF, 0.0125139.9 0.40 46.31 1.1 5.9 6.504 catalyst

The oligomer was prepared and purified in a manner as set forth inExample 4.

The average degree of polymerization was about 2 and the amount ofcyclic oligomer was less than 1% by weight based upon the total weightof polyfluorooxetane. 5-FOX is (1,1,1,2,2-pentafluoropropanoxy)methyloxetane.

As apparent from Examples MOX 4 through 6, the amount of cyclic oligomerformed, when utilizing a monoalcohol as both an initiator and a solventwithout any other solvent, was negligible, generally less than 1% byweight, whereas when a different solvent was utilized as set forth inexamples 1 through 3, the amount of cyclic oligomer was about 15% byweight.

EXAMPLE MOX 7 Synthesizing Monofunctional 9-MOX Oligomer UsingTrifluoroethanol as a Co-Initiator

Quantity (g) MW Eq mmoles density ml Substance 9-fox Monomer 45.00348.21 4.0 129.23 1.4 39.13 Trifluoroethanol, solvent 62.10 100.04 14.41620.75 1.185 52.41 Trifluoroethanol, intiator 4.31 100.04 1.00 43.081.19 3.64 BF₃THF, catalyst 2.41 139.9 0.40 17.23 1.268 1.9 Methylenechloride wash solvent 22.50 84.93 8.20 264.92 1.35 16.67 Quench (5%NaHCO3) 29.45 84.01 1.02 17.52 1.00 29.45 Wash (water) 29.45 18.01 65.741,635.00 1.00 29.45 Theroretical yield, g 50.55 Expected yield, Low42.97 Expected yield, High 48.02 solids loading, % 53.27 Max. wt %BF3THF 2.35 (incorporated as thf) ml Initial Volume 97.08 Volume after143.20 Quench Volume after Wash 90.79A 250 mL jacketed reaction flask was equipped with a condenser,temperature probe, magnetic stirrer, and addition funnel.Trifluoroethanol initiator was added (4.31 grams, 43.08 mMoles), andBF₃. THF (2.41 grams, 17.23 mMoles). The reaction was allowed to stirfor 30 minutes. 9-fox Monomer (45 grams, 129.23 mMoles) andtrifluoroethanol solvent (62.10 grams, 620.75 moles) were added over 16minutes. A maximum temperature of 34° C. was reached. The reaction wasallowed to stir at room temperature overnight. Methylene chloride (22.5g) and sodium bicarbonate (25.45 g 5%, 17.52 moles) were added to quenchthe reaction. The color changed from orange brown to yellow. The organiclayer was washed again with water. The organic solution was dried withmagnesium sulfate, and the solvent was removed to give 40.84 gramspolymer with a dp of 3.7 by NMR.

EXAMPLE MOX 8 PolyFox Mono-ol Dp 2 Procedure

Substance Scale (g) Ratio Quantity (g) MW Eq mmoles Trifluoroethanol,intiator 0.0232 10.68 100.04 1.00 106.70 BF₃THF, catalyst 0.0125 14.93139.9 1.00 106.70 5-fox Monomer 50 0.741 50.00 234.15 2.0 213.54Methylene Chloride 50.00 Trifluoroethanol, solvent 69.00 100.04 0.00Quench (5% NaHCO3) *3 100.00 methylene chloride, dilute 50.00Polymer Procedure

-   1. Oven dry reactors. Cool under N₂ purge.-   2. Use dry monomer, initiator, and solvents. To be less than 140 ppm    H₂O a piece or less than 500 ppm overall. No residual alcohol. Use    Karl Fischer analysis to determine. Can also dry with 4A molecular    sieves.-   3. Prepare initiator/catalyst complex in the dry 500 ml jacketed    flask with paddle stirrer and thermometer by stirring for 30 minutes    at 25° C.-   4. Prepare monomer or monomer/solvent solution in another flask or    WM jar.-   5. Flush micropump with appropriate solvent and set pump rate=2.4    gr/minute.-   6. Add monomer/solvent solution.-   7. Let polymer solution stir overnight at room temperature.    Workup:-   1. Dilute polymer solution with 50 ml methylene chloride.-   2. Wash polymer solution and neutralize BF3 with 100 ml 5% NaHCO3    till pH is neutral-   3. Stir and let settle to phase separate each time.-   4. Dry polymer solution over Na2SO4 for 20 minutes.-   5. Vacuum filter and rinse with methylene chloride.-   6. Rotovap off methylene chloride at 35° C. and then heat to 70° C.    to remove trifluoroethanol.-   7.

Analysis: Mass, NMR, GPC Mass=59.32 gr NMR 400 MHz in CDCl3 and excessTFAA, dp=2.4

Poly(Fluorooxetane-Ether) Block Copolymers

Block copolymers of polyfluorooxetanes and polyethers can be preparedaccording to two different routes. In one route, a polyether serves asan initiator which is reacted with fluorooxetane monomers; oralternatively, fluorooxetane oligomers, polymers, or copolymers serve asan initiator which is reacted with alkylene oxide monomers, in thepresence of a catalyst to form polyfluorooxetane blocks which are bondedor connected to the polyether, or alternatively to form polyether blockswhich are connected to the fluorooxetane oligomer, polymer, orcopolymer. The produced block copolymer is free of isocyanate groups orcompounds. The other route relates to reacting an existingpolyfluorooxetane polymer with a diisocyanate and subsequently reactingthe free isocyanate group with an existing polyether block; or toreacting an existing polyether with a diisocyanate and subsequentlyreacting the free isocyanate group with an existing polyfluorooxetaneblock.

The polyether which serves as an initiator can be made in a manner knownto the literature as well as to the art. One common source are alkyleneoxide monomers containing from 2 to about 6 carbon atoms and preferablyfrom 2 to about 4 carbon atoms. The polyether can generally have atleast one end group with two end groups being preferred such as ahydroxyl group. Suitable polyether initiators include hydroxylterminated polyethylene glycol, polypropylene glycol, polybutyleneglycol, polyisobutylene glycol, and the like as well as monohydroxylcompounds thereof such as polyethylene glycol methyl ether,polytetrahydrofuran, and the like. The number average molecular weightof such polyethers is generally from about 250 to about 10,000,desirably from about 300 to about 5,000 and preferably from about 350 toabout 2,500 and can thus be an oligomer, polymer or copolymer.

The fluorooxetane monomers are those as set forth hereinabove, which ishereby fully incorporated by reference and is shown in formulas 2A and2B where n and R are as set forth with respect to formulas 2A and 2B,and R_(f) has the indicated percent of fluorine atoms. Different R_(f)groups, i.e. mixed, can exist within the same polymer, that is,independently, have a different number of carbon atoms and such mixedR_(f) groups generally have from about 8 to about 16 carbon atoms. Thepolyfluorooxetane will generally have the following repeat groups:

where the degree of polymerization (DP) is from 2 to about 50 or about100, desirably from about 2 or about 3 to about 30, and preferably fromabout 4 to about 20 or about 25. Accordingly, the polyfluorooxetaneblock can either be an oligomer, or a polymer. Moreover, if more thanone different monomer is utilized as set forth herein below, it can be ablock copolymer.

Polymerization of the one or more fluorooxetane monomers which isinitiated by the one or more polyether functional groups such as ahydroxyl is desirably carried out via solution polymerization and thusis polymerized in the presence of a solvent. Suitable solvents aregenerally polar and/or halogenated hydrocarbons having a total from 1 toabout 6 carbon atoms such as methylene chloride, carbon tetrachloride,chloroform, trichloroethylene, chlorobenzene, ethyl bromide,dichloroethane, and the like, with methylene chloride being preferred.The amount of such solvents is generally from about 50 to about 100 anddesirably from about

50 to about 65 parts by weight for every 100 parts by weight of thepolyether initiator and the total weight of the one or morefluorooxetane monomers.

The one or more fluorooxetane monomers which are polymerized onto thepolyether initiator having 1 or more functional groups such as ahydroxyl readily polymerize in the presence of the Lewis acid catalyst(i.e. compounds capable of accepting a pair of electrons). Such suitableLewis acids include complexes of

boron trifluoride, for example BF₃etherate, BF₃-THF, antimonypentafluoride, zinc

chloride, aluminum bromide, and the like with BF₃-THF being preferred.When BF₃-THF is utilized, the THF will be polymerized and hence afluorooxetane-THF copolymer will be produced. Generally the amount ofTHF within the copolymer is from about 0.05 to about 10 or about 12 orabout 30 or about 50 percent by weight and desirably from about 0.1 toabout 5 percent by weight based upon the total weight of the copolymer.

Polymerization is carried out at temperatures of from about 15° C. to 1or 2 degrees below the boiling point of the solvent, desirably fromabout 25° C. to about 45° C., and preferably from about 35° C. to about40° C. Polymerization times can vary with regard to the temperature andother factors and generally range from about ½ to about 5 hours. Oncethe various fluorooxetane monomers have been polymerized onto thepolyether, the end product which is a block copolymer can be washed withwater to remove the solvent.

If the polyether initiator has one functional end group such as ahydroxyl, a AB block copolymer will be formed wherein the B block isderived from the fluorooxetane monomers and the A block is derived fromthe monohydroxyl polyether. Alternatively, if the polyether has twofunctional end groups, a BAB block copolymer will be formed. In eithersituation, the B block will have a hydroxyl end group.

Alternatively, a polyfluorooxetane oligomer, polymer, or copolymer,having 1 (MOX) or 2 (FOX) hydroxyl end groups, see Formulas 5A, 5B and3A, 3B respectfully, can serve as the initiator for reaction with one ormore ether forming monomers such as an alkylene oxide having from 2 toabout 6 carbon atoms and preferably from 2 to about 4 carbon atoms. Thepolyfluorooxetane oligomers, polymers, or copolymers are set forthhereinabove and for purposes of brevity, the description of the same ishereby fully incorporated by reference with the DP of the MOX being thesame as the DP of the FOX. As noted, the copolymer can be formed fromtetrahydrofuran monomers.

Polymerization conditions of the polyether forming monomers aregenerally similar to that set forth with regard to polymerization offluorooxetane monomers. Thus, the catalyst utilized are generally thesame such as Lewis acids including BF₃-THF, and the like. Polymerizationis generally carried out at temperatures from about minus 25° C. toabout 5° C. and preferably from about minus 5° C. to about 5° C.

Upon completion of polymerization, a block copolymer of apolyfluorooxetane oligomer, polymer, or copolymer with at least oneblock copolymer of a polyether will be formed wherein the polyethergenerally has an hydroxyl end group. If the polyfluorooxetane initiatoronly has one hydroxyl end group (MOX), then a BA block copolymer will beformed wherein the B block is derived from the polyfluorooxetaneinitiator and the A block is derived from the polyether monomers. If thepolyfluorooxetane initiator has two hydroxyl end groups, then an ABAblock copolymer will be formed.

An advantage of the above block copolymers is that they are free of anyundesirable isocyanate moieties which create a viscous solution, canchain extend the various block copolymers, and tend to be insoluble inwater. Generally, the block copolymers have less than about 5% byweight, desirably less than 3% by weight, and preferably less than 1% byweight or most preferably nil, that is no percent by weight, of anisocyanate containing compound therein for every 100 parts by weight ofthe formed polyether-polyfluorooxetane block copolymer.

The polyether-polyfluorooxetane block copolymers have very low surfacetensions and are generally utilized as flow, or leveling, or wettingadditives for various solutions including polymer systems such assolvent systems and preferably for aqueous systems, dispersions, oremulsions. Examples of suitable polymers which are generally soluble insolvents are known to the literature as well as to the art and generallyinclude various polyesters, various polyacrylates, variouspolyurethanes, various alkyds, various epoxies, or fluorine containingpolymers, and the like. Examples of suitable water soluble, dispersible,or emulsifiable, polymers are known to the literature as well as to theart and include various polyacetates, various polyacrylates, variouspolyacrylic acids, various polyesters, various polyethers, variouspolyurethanes, various fluorine containing polymers, and the like. Theamount of the polyfluorooxetane-polyether block copolymer additive isgenerally from about 0.001 or about 0.1 to about 1.0 or about 2.0 orabout 5 parts by weight and desirably from about 0.25 to about 0.5 partsby weight for every 100 parts by weight of the solvent soluble polymers.With regard to water soluble polymers, the amount of thepolyfluorooxetane-polyether block copolymer additive is generally from0.005 to about 0.5 or about 1.0 or about 3.0 or about 5.0 and desirablefrom about 0.01 to about 0.025 parts by weight for every 100 parts byweight of the water soluble, dispersible, or emulsifiable polymers.

The invention will be better understood by reference to the followingexamples which serve to illustrate but not to limit the presentinvention.

A. Synthesis of Poly-3-FOX-THF-Polyethylene Oxide (B-A-B)

Mole Weight G MW Moles Ratio Density ml Compound 3-FOX 50.000 184.150.27 49.98 1.150 43.5 Methylene Chloride 55.282 84.93 0.65 119.82 1.33041.6 polyethylene glycol 54.305 4000.00 0.01 2.50 1.017 53.4 BF₃THF0.760 139.90 0.01 1.00 1.268 0.6 Methylene Chloride 83.444 84.93 0.98180.86 1.330 62.7 Water 21.500 18.01 1.19 219.75 1.000 21.5 Water 42.50018.01 2.36 434.39 1.000 42.5 Theoretical Yield (g) 104.70 ExpectedYield, Low (g) 94.23 Expected Yield, High (g) 99.46 Solids LoadingReaction, % 65.52 Solids Loading Wash, % 43.10 ml Initial Volume 139.04Volume after quench, ml 223.28 Volume after wash, ml 244.28A 250 ml 3-necked jacketed reaction flask equipped with a magneticstirrer, 125 ml pressure equalizing addition funnel, nitrogen inlet andoutlet, temperature probe and reflux condenser was allowed toequilibrate at 30° C. The reactor was charged with 55.28 grams ofmethylene chloride, 54.31 grams of polyethylene glycol 4000 mw (27.15mmol OH), and 0.76 grams of boron trifluoride tetrahydrofuran complex(5.43 mmol). The reaction mixture was allowed to stir for 30 minutes. 53-FOX monomer (50.00 grams, 271.5 mmol) was added over 90 minutes. Thetemperature reached 31° C. after a 55 minute induction period. Thetemperature reached a maximum of 40° C. The reaction was allowed to stirfor 10 hours. The methylene chloride solution was then washed with 42 mlwater three times to remove the boron trifluoride tetrahydrofurancomplex. The solution was then dried with magnesium sulfate, and thesolvent was removed. Poly-3-FOX-THF-polyethylene oxide triblockcopolymer (88.25 grams) was isolated. The 3-FOX DP was 14.5 incomparison to a theoretical DP of 20.

B. Synthesis of Poly-3-FOX-THF-Polyethylene Oxide (B-A)

Mole Weight G MW Moles Ratio Density ml Compound 3-FOX 50.000 184.150.27 49.98 1.150 43.5 Methylene Chloride 38.298 84.93 0.45 83.01 1.33028.8 polyethylene glycol methyl 21.500 2000.00 0.01 1.98 1.017 21.1ether BF₃THF 0.760 139.90 0.01 1.00 1.268 0.6 Methylene Chloride 57.80884.93 0.68 125.29 1.330 43.5 Water 21.500 18.01 1.19 219.75 1.000 21.5Water 42.500 18.01 2.36 434.39 1.000 42.5 Theoretical Yield (g) 71.89Expected Yield, Low (g) 64.70 Expected Yield, High (g) 68.30 SolidsLoading Reaction, % 65.36 Solids Loading Wash, % 42.92 ml Initial Volume94.01 Volume after quench, ml 158.98 Volume after wash, ml 179.98A 250 ml 3-necked jacketed reaction flask equipped with a magneticstirrer, 125 ml pressure equalizing addition funnel, Argon inlet andoutlet, temperature probe and reflux condenser was allowed toequilibrate at 33° C. The reactor was charged with 26.5 grams ofmethylene chloride, 21.5 grams of polyethylene glycol monomethyl ether2000 mw (10.75 mmol OH), and 0.76 grams of boron trifluoridetetrahydrofuran complex (5.43 mmol). The reaction mixture was allowed tostir for 30 minutes. 3-FOX monomer (50.0 grams, 271.5 mmol) was addedover 50 minutes. The temperature reached 38.5° C. after a 30 minuteinduction period. The temperature reached a maximum of 42.8° C. Thereaction was allowed to stir for 10 hours. The methylene chloridesolution was then washed with 42 ml water three times to remove theboron trifluoride tetrahydrofuran complex. The solution was then driedwith magnesium sulfate, and the solvent was removed.Poly-3-FOX-THF-polyethylene oxide diblock copolymer (59.05 grams) wasisolated. The 3-FOX DP was 21.04 in comparison to a theoretical DP of20.0.

C. Synthesis of Poly-3-FOX-THF-Polyethylene Oxide (B-A)

Mole Weight G MW Moles Ratio Density ml Compound 3-FOX 50.000 184.150.27 15.10 1.150 43.5 Methylene Chloride 74.200 84.93 0.87 48.60 1.33055.8 polyethylene glycol methyl ether 90.000 2000.00 0.05 2.50 1.01788.5 BF₃THF 2.515 139.90 0.0180 1.00 1.268 2.0 Methylene Chloride119.000 84.93 1.40 77.94 1.330 89.5 5% sodium bicarbonate 21.500 84.010.0128 0.71 1.000 21.5 Water 42.500 18.01 2.36 131.27 1.000 42.5Theoretical Yield (g) 141.30 Expected Yield, Low (g) 127.17 ExpectedYield, High (g) 134.23 Solids Loading Reaction, % 65.76 Solids LoadingWash, % 42.45 ml Initial Volume 189.75 Volume after quench, ml 300.72Volume after wash, ml 321.72A 250 ml 3-necked jacketed reaction flask equipped with a magneticstirrer, 125 ml pressure equalizing addition funnel, argon inlet andoutlet, temperature probe and reflux condenser was allowed toequilibrate at 33° C. The reactor was charged with 74.89 grams ofmethylene chloride, 90 grams of polyethylene glycol monomethyl ether2000 mw (45 mmol OH), and 2.51 grams of boron trifluoridetetrahydrofuran complex (17.94 mmol). The reaction mixture was allowedto stir for 30 minutes. 3-FOX monomer of (50.0 grams, 271.5 mmol) wasadded over 45 minutes. The temperature reached 36.1° C. after a 25minute induction period. The temperature reached a maximum of 37° C. Thereaction was allowed to stir for 10 hours. The methylene chloridesolution was then washed with 42 ml water three times to remove theboron trifluoride tetrahydrofuran complex. The solution was then driedwith magnesium sulfate, and the solvent was removed.Poly-3-FOX-THF-polyethylene oxide diblock copolymer (113.69 grams) wasisolated. The 3-FOX DP was 10.5 in comparison to a theoretical DP of 6.

D. Synthesis of Poly-3-FOX-THF-Polyethylene Oxide (B-A)

Mole Weight G MW Moles Ratio Density ml Compound 3-FOX 1000.000 184.155.43 10.00 1.150 869.6 Methylene Chloride 781.833 84.93 9.21 16.95 1.330587.8 Carbowax (TM) PEO 350 Monol 475.156 350.00 1.36 2.50 1.017 467.2BF₃THF 75.970 139.90 0.5430 1.00 1.268 59.9 Methylene Chloride 1961.95784.93 23.10 42.54 1.330 1475.2 5% Sodium Bicarbonate 540.000 84.01 0.320.59 1.000 540.0 Wash (water) 272.110 18.01 15.11 27.82 1.000 272.1Theoretical Yield (g) 1514.31 Expected Yield, Low (g) 1362.88 ExpectedYield, High (g) 1438.59 Solids Loading Reaction, % 66.49 Solids LoadingWash, % 36.12 ml Initial Volume 1984.54 Volume after quench, ml 3999.69Volume after wash, ml 3731.80A 4 liter 3-necked jacketed reaction flask equipped with a mechanicalstirrer, monomer addition pump, nitrogen inlet and outlet, temperatureprobe and reflux condenser was allowed to equilibrate at 35° C. Thereactor was charged with 781.33 grams of methylene chloride, 475.16grams of polyethylene glycol monomethyl ether 350 mw (1.36 mol OH), and75.97 grams of boron trifluoride tetrahydrofuran complex (0.543 mol).The reaction mixture was allowed to stir for 30 minutes. 3-FOX monomer(1000 grams, 5.43 mol) was added over 2 hours 30 minutes. Thetemperature reached 35.6° C. after a 25 minute induction period. Thetemperature reached a maximum of 42° C. The reaction was allowed to stirfor 2 hours. Additional methylene chloride was added (1180 grams)and thesolution was then washed with 750 ml 5% sodium bicarbonate two times and272 ml water to remove the boron trifluoride tetrahydrofuran complex.The solution was then dried with magnesium sulfate, and the solvent wasremoved. Poly-3-FOX-THF-polyethylene oxide diblock copolymer, DP 3.9(1490 grams) was isolated.

E. Synthesis of Poly-3-FOX-THF-Polypropylene Oxide (B-A-B)

Mole Weight G MW Moles Ratio Density ml Compound 3-FOX 535.000 184.152.91 30.00 1.150 465.2 Methylene Chloride 541.601 84.93 6.38 65.84 1.330407.2 PPG voranol 220-056 486.890 2011.10 0.24 2.50 1.017 478.8 BF₃THF13.550 139.90 0.0969 1.00 1.268 10.7 Methylene Chloride 817.512 84.939.63 99.38 1.330 614.7 5% Sodium Bicarbonate 830.000 84.01 0.49 5.101.000 830.0 Wash (water) 819.995 18.01 45.53 470.09 1.000 820.0Theoretical Yield (g) 1028.87 Expected Yield, Low (g) 925.99 ExpectedYield, High (g) 977.43 Solids Loading Reaction, % 65.66 Solids LoadingWash, % 43.24 ml Initial Volume 1361.87 Volume after quench, ml 3210.90Volume after wash, ml 2586.23A 4 liter 3-necked jacketed reaction flask equipped with a mechanicalstirrer, monomer addition pump, nitrogen inlet and outlet, temperatureprobe and reflux condenser was allowed to equilibrate at 25° C. Thereactor was charged with 541.60 grams of methylene chloride, 486.89grams of voranol polypropylene glycol 220-056 (Purchased from Dow, 0.24mol OH), and 13.55 grams of boron trifluoride tetrahydrofuran complex(0.0979 mol). The reaction mixture was allowed to stir for 30 minutes.3-FOX monomer (535 grams, 2.91 mol) was added over 1 hour 47 minutes.The temperature reached 25.6° C. after a 10 minute induction period. Thetemperature reached a maximum of 32° C. The reaction was allowed to stirfor 10 hours. Additional methylene chloride was added (817.52 grams),and the solution was then washed with 820 ml 5% sodium bicarbonate twotimes and 535 ml water to remove the boron trifluoride tetrahydrofurancomplex. The solution was then dried with magnesium sulfate, and thesolvent was removed. Poly-3-FOX-THF-Polypropylene Oxide triblockcopolymer, DP 13.8 (981.8 grams) was isolated. GPC: Mn=3080, Mw=5040(Polystyrene standards, AO # 14527). Hydroxyl Number determination: meanOH number 32.90 Mn 3410.33

F. Synthesis of Poly-3-FOX-THF-Polypropylene Oxide (B-A-B)

Mole Weight G MW Moles Ratio □ ml Compound 3-FOX 700.000 184.15 3.8030.00 1.150 608.7 Methylene Chloride 537.881 84.93 6.33 49.98 1.330404.4 PPG voranol 220-056 314.870 2011.10 0.16 1.24 1.017 309.6 BF₃THF17.729 139.90 0.1267 1.00 1.268 14.0 Methylene Chloride 811.896 84.939.56 75.44 1.330 610.4 5% Sodium Bicarbonate 700.000 84.01 0.42 3.291.000 700.0 Wash (water) 700.000 18.01 38.87 306.70 1.000 700.0Theoretical Yield (g) 1024.01 Expected Yield, Low (g) 921.61 ExpectedYield, High (g) 972.81 Solids Loading Reaction, % 65.75 Solids LoadingWash, % 43.34 ml Initial Volume 1336.71 Volume after quench, ml 3051.51Volume after wash, ml 2441.07A 4 liter 3-necked jacketed reaction flask equipped with a mechanicalstirrer, monomer addition pump, nitrogen inlet and outlet, temperatureprobe and reflux condenser was allowed to equilibrate at 25° C. Thereactor was charged with 537.8 grams of methylene chloride, 314.8 gramsof voranol polypropylene glycol 220-056 (purchased from Dow, 0.156 molOH), and 17.73 grams of boron trifluoride tetrahydrofuran complex(0.1267 mol). The reaction mixture was allowed to stir for 30 minutes.3-FOX monomer (700 grams, 3.80 mol) was added over 1 hours 10 minutes.The temperature reached 29° C. after a 7 minute induction period. Thetemperature reached a maximum of 32° C. The reaction was allowed to stirfor 10 hours. Additional methylene chloride was added (811.90 grams),and the solution was then washed with 820 ml 5% sodium bicarbonate twotimes and 750 ml water to remove the boron trifluoride tetrahydrofurancomplex. The solution was then dried with magnesium sulfate, and thesolvent was removed. Poly-3-FOX-THF-Polypropylene Oxide triblockcopolymer, DP 22.1 (1012.3 grams) was isolated. GPC: Mn=4340, Mw=7680(polystyrene standards, AO # 14527). Hydroxyl Number determination: OH #22.38, Mn=5013.

G. Synthesis of Poly-3-FOX-THF-Polybutylene Oxide (B-A-B)

Mole Weight G MW Moles Ratio Density ml Compound 3-FOX 100.000 184.150.54 15.00 1.150 87.0 Methylene Chloride 100.700 84.93 1.19 32.75 1.33075.7 B100-1000 90.506 1000.00 0.09 2.50 1.017 89.0 BF₃THF 5.065 139.900.04 1.00 1.268 4.0 Methylene Chloride 172.400 84.93 2.03 56.07 1.330129.6 Water 43.000 18.01 2.39 65.95 1.000 43.0 Water 85.000 18.01 4.72130.37 1.000 85.0 Theoretical Yield (g) 193.12 Expected Yield, Low (g)173.80 Expected Yield, High (g) 183.46 Solids Loading Reaction, % 66.01Solids Loading Wash, % 41.73 ml Initial Volume 255.66 Volume afterquench, ml 428.28 Volume after wash, ml 470.28A 1 liter 3-necked jacketed reaction flask equipped with a magneticstirrer, addition funnel, nitrogen inlet and outlet, temperature probeand reflux condenser was allowed to equilibrate at 25° C. The reactorwas charged with 100.7 grams of methylene chloride, 90.51 grams ofB100-1000 polybutylene glycol (Dow, 0.09 mol OH), and 5.07 grams ofboron trifluoride tetrahydrofuran complex (0.04 mol). The reactionmixture was allowed to stir for 30 minutes. 3-FOX monomer (100 grams,0.54 mol) was added over 30 minutes. The temperature reached 35° C.after a 5 minute induction period. The temperature reached a maximum of60° C. The reaction was allowed to stir for 10 hours. Additionalmethylene chloride was added (172.4 grams), and the solution was thenwashed with 85 ml 5% sodium bicarbonate and 85 ml water to remove theboron trifluoride tetrahydrofuran complex. The solution was then driedwith magnesium sulfate, and the solvent was removed.Poly-3-FOX-THF-Polybutylene Oxide triblock copolymer, DP 13.83 (185grams) was isolated.

H. Synthesis of Poly-3-FOX-Polytetrahydrofuran (B-A)

Mole Weight G MW Moles Ratio density ml Compound 3-FOX 535.000 184.152.91 30.00 1.150 465.2 Methylene Chloride 537.798 84.93 6.33 65.38 1.330404.4 Terathane 2000 poly THF 495.680 2047.40 0.24 2.50 1.017 487.4BF₃THF 13.550 139.90 0.0969 1.00 1.268 10.7 Methylene Chloride 824.54484.93 9.71 100.24 1.330 620.0 5% Sodium Bicarbonate 535.000 84.01 0.323.29 1.000 535.0 Wash (water) 535.000 18.01 29.71 306.70 1.000 535.0Theoretical Yield (g) 1037.66 Expected Yield, Low (g) 933.90 ExpectedYield, High (g) 985.78 Solids Loading Reaction, % 66.01 Solids LoadingWash, % 43.39 ml Initial Volume 1367.66 Volume after quench, ml 2522.62Volume after wash, ml 1902.66A 4 liter 3-necked jacketed reaction flask equipped with a mechanicalstirrer, monomer addition pump, nitrogen inlet and outlet, temperatureprobe and reflux condenser was allowed to equilibrate at 25° C. Thereactor was charged with 537.8 grams of methylene chloride, 495.68 gramsof Terathane polyTHF 2000 (Purchased from Dupont, 0.2421 mol OH), and13.55 grams of boron trifluoride tetrahydrofuran complex (0.09684 mol).The reaction mixture was allowed to stir for 30 minutes. 3-FOX monomer(535 grams, 2.91 mol) was added over 2 hours 30 minutes. The temperaturereached 26.7° C. after a 40 minute induction period. The temperaturereached a maximum of 27° C. The reaction was allowed to stir for 3hours. Additional methylene chloride was added (824.55 grams), and thesolution was then washed with 860 ml 5% sodium bicarbonate and 890 mlwater to remove the boron trifluoride tetrahydrofuran complex. Thesolution was then dried with magnesium sulfate, and the solvent wasremoved. Poly-3-FOX-THF-Polytetrahydrofuran diblock copolymer, DP 11.04(979.8 grams) was isolated. GPC: Mn=3970, Mw=8090 (polystyrenestandards, AO # 14527). Hydroxyl Number determination: OH # 41.93,Mn=2676.

I. Synthesis of Poly-5-FOX-THF(DP 20)-Polyethylene Oxide (B-A)

Mole Weight G MW Moles Ratio Density ml Compound 5-FOX 100.000 234.150.43 50.21 1.150 87.0 Methylene Chloride 56.959 84.93 0.67 78.84 1.33042.8 Carbowax (TM) PEO 350 Monol 7.470 350.00 0.02 2.51 1.017 7.3 BF₃THF1.190 139.90 0.0085 1.00 1.268 0.9 Methylene Chloride 85.976 84.93 1.01119.01 1.330 64.6 5% Sodium Bicarbonate 100.000 84.01 0.06 7.00 1.000100.0 Wash (water) 100.000 18.01 5.55 652.77 1.000 100.0 TheoreticalYield (g) 108.08 Expected Yield, Low (g) 97.27 Expected Yield, High (g)102.68 Solids Loading Reaction, % 65.61 Solids Loading Wash, % 43.19 mlInitial Volume 138.07 Volume after quench, ml 302.71 Volume after wash,ml 302.71A 500 milliliter 3-necked reaction flask equipped with a magneticstirrer, monomer addition funnel, nitrogen inlet and outlet, temperatureprobe and reflux condenser was allowed to equilibrate at 25° C. Thereactor was charged with 56.96 grams of methylene chloride, 7.47 gramsof polyethylene glycol monomethyl ether 350 mw (21.35 mmol OH), and 1.19grams of boron trifluoride tetrahydrofuran complex (8.54 mmol). Thereaction mixture was allowed to stir for 30 minutes. 5-FOX monomer (100grams, 427.08 mmol) was added over 2 hours 35 minutes. The temperaturereached 29.4° C. after a 10 minute induction period. A DP of 9.13 wasfound. An additional 109.99 grams of 5-FOX monomer was added. Thetemperature reached a maximum of 30.6° C. The reaction was allowed tostir for 10 hours. Additional methylene chloride was added (85.98 grams)and the solution was then washed with 100 ml 5%o sodium bicarbonate and100 ml water to remove the boron trifluoride tetrahydrofuran complex.The solution was then dried with magnesium sulfate, and the solvent wasremoved. Poly-5-FOX-THF(DP 20)-Polyethylene Oxide diblock copolymer, DP20.6 (195.5 grams) was isolated.

J. Synthesis of Poly-5-FOX-THF(DP 6)-Polyethylene Oxide (B-A)

Mole Weight G MW Moles Ratio Density ml Compound 5-FOX 100.000 234.150.43 15.01 1.150 87.0 Methylene Chloride 66.202 84.93 0.78 27.40 1.33049.8 Carbowax (TM) PEO 350 Monol 24.910 350.00 0.07 2.50 1.017 24.5BF₃THF 3.980 139.90 0.0284 1.00 1.268 3.1 Methylene Chloride 99.92884.93 1.18 41.36 1.330 75.1 5% Sodium Bicarbonate 100.000 84.01 0.062.09 1.000 100.0 Wash (water) 100.000 18.01 5.55 195.17 1.000 100.0Theoretical Yield (g) 126.96 Expected Yield, Low (g) 114.27 ExpectedYield, High (g) 120.61 Solids Loading Reaction, % 66.07 Solids LoadingWash, % 43.69 ml Initial Volume 164.37 Volume after quench, ml 339.50Volume after wash, ml 339.50A 500 milliliter 3-necked reaction flask equipped with a magneticstirrer, monomer addition funnel, nitrogen inlet and outlet, temperatureprobe and reflux condenser was allowed to equilibrate at 25° C. Thereactor was charged with 66.20 grams of methylene chloride, 24.91 gramsof polyethylene glycol monomethyl ether 350 mw (71.18 mmol OH), and 3.98grams of boron trifluoride tetrahydrofuran complex (28.47 mmol). Thereaction mixture was allowed to stir for 30 minutes. 5-FOX monomer (100grams, 427.08 mmol) was added over 23 minutes. The temperature reached31° C. after a 10 minute induction period. The temperature reached amaximum of 33° C. The reaction was allowed to stir for 10 hours.Additional methylene chloride was added (99.93 grams) and the solutionwas then washed with 100 ml 5% sodium bicarbonate and 100 ml water toremove the boron trifluoride tetrahydrofuran complex. The solution wasthen dried with magnesium sulfate, and the solvent was removed.Poly-5-FOX-THF(DP 6)-Polyethylene Oxide diblock copolymer, DP 5.3 (115.5grams) was isolated.

K. Synthesis of Poly-5-FOX-THF(DP 8)-Polyethylene Oxide (B-A-B)

Mole Weight G MW Moles Ratio Density ml Compound 5-FOX 1200.000 234.155.12 20.00 1.150 1043.5 Methylene Chloride 929.999 84.93 10.95 42.731.330 699.2 PEO 400 diol 256.248 400.00 0.64 2.50 1.017 252.0 BF₃THF35.850 139.90 0.2563 1.00 1.268 28.3 5% Sodium Bicarbonate 1200.00084.01 0.71 2.79 1.000 1200.0 Wash (water) 1200.000 18.01 66.63 260.011.000 1200.0 Theoretical Yield (g) 1474.72 Expected Yield, Low (g)1327.25 Expected Yield, High (g) 1400.99 Solids Loading Reaction, %61.60 ml Initial Volume 2022.96 Volume after quench, ml 3222.96 Volumeafter wash, ml 3222.96A 4 liter 3-necked reaction flask equipped with a mechanical stirrer,monomer addition pump, nitrogen inlet and outlet, temperature probe andreflux condenser was allowed to equilibrate at 35° C. The reactor wascharged with 930.00 grams of methylene chloride, 256.25 grams ofpolyethylene glycol 400 mw (purchased from Dow, 640.61 mmol OH), and35.85 grams of boron trifluoride tetrahydrofuran complex (256.26 mmol).The reaction mixture was allowed to stir for 50 minutes. 5-FOX monomer(1200 grams, 5124 mmol) was added over 1 hour and 25 minutes. Thetemperature reached 31° C. after a 10 minute induction period. Thetemperature reached a maximum of 43.8° C. The reaction was allowed tostir for 2 hours. The solution was then washed with 1200 ml 5% sodiumbicarbonate and 1200 ml water to remove the boron trifluoridetetrahydrofuran complex. The solution was then dried with magnesiumsulfate, and the solvent was removed. Poly-5-FOX-THF(DP 8)-PolyethyleneOxide triblock copolymer, DP 8.23 (1419.1 grams) was isolated.

L. Synthesis of Poly-9-FOX-THF (DP 6)-Polyethylene Oxide (B-A)

Mole Weight G MW Moles Ratio Density ml Compound 9-FOX 75.000 348.210.22 14.99 1.150 65.2 Methylene Chloride 46.407 84.93 0.55 38.03 1.33034.9 Carbowax (TM) PEO 350 Monol 12.560 350.00 0.04 2.50 1.017 12.4BF₃THF 2.010 139.90 0.0144 1.00 1.268 1.6 Methylene Chloride 70.04884.93 0.82 57.41 1.330 52.7 5% Sodium Bicarbonate 75.000 84.01 0.04 3.111.000 75.0 Wash (water) 75.000 18.01 4.16 289.85 1.000 75.0 TheoreticalYield (g) 88.60 Expected Yield, Low (g) 79.74 Expected Yield, High (g)84.17 Solids Loading Reaction, % 65.87 Solids Loading Wash, % 43.48 mlInitial Volume 114.04 Volume after quench, ml 241.71 Volume after wash,ml 241.71A 250 milliliter 3-necked reaction flask equipped with a magneticstirrer, monomer addition funnel, nitrogen inlet and outlet, temperatureprobe and reflux condenser was allowed to equilibrate at 25° C. Thereactor was charged with 46.41 grams of methylene chloride, 12.56 gramsof polyethylene glycol monomethyl ether 350 mw (35.90 mmol OH), and 2.01grams of boron trifluoride tetrahydrofuran complex (14.36 mmol). Thereaction mixture was allowed to stir for 30 minutes. 9-FOX monomer (75grams, 215.39 mmol) was added over 2 hours. The temperature reached26.1° C. after a 15 minute induction period. The temperature reached amaximum of 29.4° C. The reaction was allowed to stir for 2 hours.Additional methylene chloride was added (75 grams) and the solution wasthen washed with 75 ml 5% sodium bicarbonate and 75 ml water to removethe boron trifluoride tetrahydrofuran complex. The solution was thendried with magnesium sulfate, and the solvent was removed.Poly-9-FOX-THF (DP 6)-Polyethylene Oxide diblock copolymer, DP 6.14(66.7 grams) was isolated.

M. Synthesis of Poly-9-FOX-THF (DP 20)-Polyethylene Oxide (B-A)

Mole Weight G MW Moles Ratio Density ml Compound 9-FOX 75.000 348.210.22 50.22 1.150 65.2 Methylene Chloride 41.748 84.93 0.49 114.62 1.33031.4 Carbowax (TM) PEO 350 Monol 3.770 350.00 0.01 2.51 1.017 3.7 BF₃THF0.600 139.90 0.0043 1.00 1.268 0.5 Methylene Chloride 63.016 84.93 0.74173.00 1.330 47.4 5% Sodium Bicarbonate 75.000 84.01 0.04 10.41 1.00075.0 Wash (water) 75.000 18.01 4.16 970.99 1.000 75.0 Theoretical Yield(g) 79.08 Expected Yield, Low (g) 71.17 Expected Yield, High (g) 75.13Solids Loading Reaction, % 65.53 Solids Loading Wash, % 43.10 ml InitialVolume 100.79 Volume after quench, ml 223.17 Volume after wash, ml223.17A 250 milliliter 3-necked reaction flask equipped with a magneticstirrer, monomer addition funnel, nitrogen inlet and outlet, temperatureprobe and reflux condenser was allowed to equilibrate at 25° C. Thereactor was charged with 41.75 grams of methylene chloride, 3.77 gramsof polyethylene glycol monomethyl ether 350 mw (10.77 mmol OH), and 0.60grams of boron trifluoride tetrahydrofuran complex (4.31 mmol). Thereaction mixture was allowed to stir for 30 minutes. 9-FOX monomer (75grams, 215.39 mmol) was added over 2 hours 35 minutes. The temperaturereached 29.4° C. after a 10 minute induction period. A DP of 9.13 wasfound. An additional 109.99 grams of 5-FOX monomer was added. Thetemperature reached a maximum of 30.6° C. The reaction was allowed tostir for 10 hours. Additional methylene chloride was added (75 grams)and the solution was then washed with 75 ml 5% sodium bicarbonate and 75ml water to remove the boron trifluoride tetrahydrofuran complex. Thesolution was then dried with magnesium sulfate, and the solvent wasremoved. Poly-9-FOX-THF (DP 20)-Polyethylene Oxide diblock copolymer, DP19.96 (63.6 grams) was isolated.

N. Synthesis of Poly-Mixed-FOX-THF (DP 6)-Polyethylene Oxide (B-A)

Weight Mole (SxRatio) G MW Moles Ratio Density ml Compound Zox Monomer100.000 579.00 0.17 15.01 1.150 87.0 Heloxy 7, 5 mol % 1.970 228.000.009 0.75 0.900 Benzotrifluoride 100.000 146.11 0.68 59.47 1.185 84.4Carbowax (TM) PEO 350 10.070 350.00 0.03 2.50 1.017 9.9 Monol BF₃THF1.610 139.90 0.0115 1.00 1.268 1.3 Methylene chloride, initiator 23.11584.93 0.27 23.65 1.330 17.4 solvent Methylene chloride, wash 88.05684.93 1.04 90.09 1.330 66.2 solvent 5% Sodium Bicarbonate 100.000 84.010.06 5.17 1.000 100.0 Wash (water) 100.000 18.01 5.55 482.48 1.000 100.0Theoretical Yield (g) 110.90 Expected Yield, Low (g) 99.81 ExpectedYield, High (g) 105.35 Solids Loading Reaction, % 52.76 Solids LoadingWash, % 37.26 ml Initial Volume 182.52 Volume after quench, ml 366.10Volume after wash, ml 366.10A 500 milliliter 3-necked reaction flask equipped with a magneticstirrer, monomer addition funnel, nitrogen inlet and outlet, temperatureprobe and reflux condenser was allowed to equilibrate at 25° C. Thereactor was charged with 23.12 grams of methylene chloride, 10.07 gramsof polyethylene glycol monomethyl ether 350 mw (28.79 mmol OH), and 1.61grams of boron trifluoride tetrahydrofuran complex (11.31 mmol). Thereaction mixture was allowed to stir for 30 minutes. A solutioncontaining ZOX monomer mixtures of different fluorinated oxetanemonomers, wherein, independently R_(f) has from 8 to 16 carbon atoms,(100 grams, 172.71 mmol), heloxy 7 (1.97 grams, 8.64 mmol), and 100 mlof benzotrifluoride was added over 30 minutes. The temperature reached26.6° C. after a 10 minute induction period. The temperature reached amaximum of 30.6° C. The reaction was allowed to stir for 4 hours.Additional methylene chloride was added (88.06 grams) and the solutionwas then washed with 100 ml 5% sodium bicarbonate and 100 ml water toremove the boron trifluoride tetrahydrofuran complex. The solution wasthen dried with magnesium sulfate, and the solvent was removed.Poly-Mixed-FOX-THF (DP 6)-Polyethylene Oxide diblock copolymer, DP 5.90(104.1 grams) was isolated.

O. Synthesis of Poly-Mixed-FOX-THF (DP20)-Polyethylene Oxide (B-A)

Weight Moles (SxRatio) G MW Moles Ratio Density ml Compound Zox Monomer100.000 579.00 0.17 50.34 1.150 87.0 Heloxy 7, 5 mol % 1.970 228.000.009 2.52 0.900 Benzotrifluoride 100.000 146.11 0.68 199.48 1.185 84.4Carbowax (TM) PEO 350 Monol 3.020 350.00 0.01 2.51 1.017 3.0 BF₃THF0.480 139.90 0.0034 1.00 1.268 0.4 Methylene chloride, initiator 21.63484.93 0.25 74.24 1.330 16.3 solvent Methylene chloride, wash 82.41684.93 0.97 282.83 1.330 62.0 solvent 5% Sodium Bicarbonate 100.000 84.010.06 17.35 1.000 100.0 Wash (water) 100.000 18.01 5.55 1618.31 1.000100.0 Theoretical Yield (g) 103.27 Expected Yield, Low (g) 92.94Expected Yield, High (g) 98.10 Solids Loading Reaction, % 50.86 SolidsLoading Wash, % 36.20 ml Initial Volume 174.69 Volume after quench, ml352.93 Volume after wash, ml 352.93A 500 milliliter 3-necked reaction flask equipped with a magneticstirrer, monomer addition funnel, nitrogen inlet and outlet, temperatureprobe and reflux condenser was allowed to equilibrate at 25° C. Thereactor was charged with 21.63 grams of methylene chloride, 3.02 gramsof polyethylene glycol monomethyl ether 350 mw (8.64 mmol OH), and 0.48grams of boron trifluoride tetrahydrofuran complex (3.45 mmol). Thereaction mixture was allowed to stir for 30 minutes. A solutioncontaining ZOX monomer (100 grams, 172.71 mmol), heloxy 7 (1.97 grams,8.64 mmol), and 100 ml of benzotrifluoride was added over 30 minutes.The temperature reached 26.6° C. after a 10 minute induction period. Thetemperature reached a maximum of 30.6° C. The reaction was allowed tostir for 4 hours. Additional methylene chloride was added (82.42 grams)and the solution was then washed with 100 ml 5% sodium bicarbonate and100 ml water to remove the boron trifluoride tetrahydrofuran complex.The solution was then dried with magnesium sulfate, and the solvent wasremoved. Poly-Mixed-FOX-THF (DP20)-Polyethylene Oxide diblock copolymerDP 19.55 (77.8 grams) was isolated.

Polyfluorooxetane-Urethane Polyether Block Copolymers

Block copolymers are formed by initially reacting a fluorooxetaneoligomer, polymer, or copolymer, having either 1 or 2 hydroxyl endgroups with generally excess moles of a polyisocyanate to form aurethane linkage having a free isocyanate end group which issubsequently reacted with excess moles of a polyether. Alternatively,the block copolymers can be formed by initially reacting a polyetherhaving either 1 or 2 hydroxyl end groups with generally excess moles ofa polyisocyanate to form a urethane linkage having a free isocyanate endgroup which is subsequently reacted with excess moles of a fluorooxetaneoligomer, polymer or copolymer.

A polyfluorooxetane polymer is made in a manner as set forth hereinaboveand the same is hereby fully incorporated by reference. As previouslynoted, the description of the same is also in U.S. Pat. Nos. 5,650,483;5,668,250; 5,668,251; or 5,663,289; which are hereby fully incorporatedby reference. The polyfluorooxetane if polymerized utilizing amonoalcohol will only have one terminal hydroxyl group (MOX) as informulas 5A and 5B hereby fully incorporated by reference, whereas ifpolymerized utilizing a diol or glycol initiator will have two terminalhydroxyl groups (FOX) see formulas 3A and 3B, also as set forth hereinand fully incorporated by reference. In either event, the repeat unit ofthe polymer will have the structure as set forth in formulas 2AA and 2BBas follows:

wherein n and R are as set forth therein, wherein each R_(f) within thepolymer can be the same or different and independently is linear orbranched, unsaturated or preferably a saturated alkyl group having from1 to about 20 carbon atoms with from about 1 to about 5, 7 or 9 carbonatoms being preferred with a minimum 25, 50, 75, 80, 85, 90 or 95percent, or preferably perfluorinated i.e. 100 percent of the H atoms ofsaid R_(f) being replaced by F, and optionally up to all of theremaining H atoms being replaced by I, Cl or Br. When thepolyfluorooxetane is made from a glycol or diol initiator, or amonoalcohol initiator, the DP is generally from about 2 or about 3 toabout 50 or about 100, and desirably from about 4 or about 5 to about 20or about 30. The polymerization of the fluorooxetane monomers, as notedabove, is generally carried out in a catalyst such as a borontrifluoride tetrahydrofuran complex in the presence of a halogensolvent. When BF₃-THF is utilized, a small amount of the tetrahydrofuranis incorporated into the FOX or MOX oligomer, or polymer such as acopolymer is formed wherein from about 0.1% to about 10% or about 25% byweight and desirably from about 0.1% to about 6% by weight is thetetrahydrofuran. The reaction temperature is generally from about 15° C.or 20° C. to about 70° C. or 80° C. and preferably from about 35° C. toabout 45° C.

The polyisocyanate can generally contain from 2 to about 4 isocyanategroups with two groups, that is diisocyanate being highly preferred. Thevarious polyisocyanates have the formula R—(NCO)_(n) wherein n is 2, 3or 4 with 2 being preferred and R is an aliphatic having from 4 to about25 carbon atoms, or an aromatic, or an alkyl substituted aromatic, etc.having a total of 6 to about 30 carbon atoms. Specific examples ofsuitable diisocyanates include hexamethylene diisocyanate (HDI),isophorone diisocyanate (IPDI) preferred, methylene diphenylisocyanate(MDI), polymeric MDI, toluene diisocyanate (TDI), polymeric HDI,cyclohexylene-1,4-diisocynate, 2,2,4-trimethylhexmethylene diisocyanate,and the like. The equivalent ratio of the total isocyanate groups to thetotal hydroxyl end group(s) of the polyfluorooxetane is generally about2.0, that is from about 1.9 to about 2.15 and preferably from about 2.0to 2.05. The reaction between the diisocyanate and the hydroxylterminated polyfluorooxetane polymer is generally carried out in thepresence of a isocyanate catalyst at a reaction temperature of fromabout 45° C. to about 85° C. and preferably from about 55° C. to about75° C. Examples of suitable tin catalysts include dibutyltin dilaurate,stannous octoate, and the like. Due to the essentially 2 to 1 equivalentratio of diisocyanate to hydroxyl end groups, each terminal hydroxyl endgroup of the polyFOX or MOX polymer will react with a diisocyanate andform a urethane linkage and thus leave a free isocyanate end group. Thereaction is desirably carried out in the absence of any solvent orwater.

Various hydroxyl terminated polyethers are then reacted with theisocyanate terminated FOX or MOX polymer at the same reaction conditionsas set forth in the preceding paragraph. The various polyethers areadded all at once so that a block copolymer is formed rather than topermit the polyether to act as a chain extender. The amount of polyetheradded is generally an equivalent weight ratio of 2 based upon each freeisocyanate end groups so that a great majority of the isocyanate endgroups react with a polyether and form a block copolymer having ahydroxyl end group. If the polyfluorooxetane polymer has 2 hydroxyl endgroups, an ABA block copolymer will be formed. If the polyfluorooxetanepolymer has only 1 hydroxyl end group, then a BA block copolymer will beformed where B is the polyfluorooxetane polymer and A is the polyetherpolymer. In either event, the blocks will be connected by a diisocyanategroup and hence by a urethane linkage.

The hydroxyl terminated polyethers contain repeat units having from 2 toabout 6 and desirably from 2 to about 3 carbon atoms such aspolyethylene oxide, polypropylene oxide, polybutylene oxide, and thelike. The polyether can either have one or two hydroxyl end groups. Thenumber average molecular weight of various polyethers is generally fromabout 200 to about 5,000 with from about 350 to about 1,000 or 2,000being preferred.

Alternatively, a polyether block copolymer as set forth above havingeither 1 or 2 hydroxyl end groups can be reacted with an excess of apolyisocyanate such as a diisocyanate. In other words, the reactionconditions including temperature, the excess amount of thepolyisocyanate, and the like are the same as set forth hereinimmediately above and is hereby fully incorporated by reference. Oncethe polyisocyanate has been reacted with the polyether thereby forming aurethane linkage and at least one free isocyanate end group, theremaining end group is reacted with a polyfluorooxetane block copolymerwhich can be an oligomer, a polymer, or a copolymer as noted hereinaboveand fully incorporated by reference. The reaction conditions aregenerally the same as set forth hereinabove and are hereby fullyincorporated by reference. In this scenario, if the polyether has twohydroxyl end groups, a BAB block copolymer will be formed. If thepolyether block copolymer has only one hydroxyl end group, then an ABblock copolymer will be formed. In either event, the blocks will beconnected by a polyisocyanate group and hence by a urethane linkage.

The polyfluorooxetane-urethane polyether block copolymers have very lowsurface tension and serve as useful flow, or leveling, or wetting agentsas for use with solutions such as aqueous systems, dispersions, oremulsions, or preferably solvent polymer solutions. Suitable aqueoussoluble, dispersible, or emulsifiable polymers include variouspolyesters, various polyurethanes, various polyethers, variouspolyesters, various polyacetates, various polyacrylics or polyacrylates,or

fluorine containing polymers and the like. Suitable solvent polymersinclude various polyesters, various polyacrylates, variouspolyurethanes, various alkyds, various epoxies, or various fluorinecontaining polymers, and the like. When utilized, the amount of theflow, or leveling, or wetting agent is generally from about 0.001, orabout 0.1, to about 1.0, or about 2.0, or about 5.0 parts, andpreferably from about 0.25 to about 0.5 parts by weight for every 100parts by weight of the solvent soluble polymer. With regard to watersoluble polymers, the amount of the polyfluorooxetane-polyether blockcopolymer additive is generally from 0.0005 or from about 0.005 to about0.1, or about 0.5, or about 1.0, or about 3.0, or about 5.0 parts anddesirably from about 0.01 to about 0.025 parts by weight for every 100parts by weight of the water soluble or water dispersible polymers.

The invention will be better understood by reference to the followingexamples which serve to illustrate, but not to limit the presentinvention.

EXAMPLE 1 Synthesis of Poly-5-MOX-Diiso-Polyethylene Oxide Ether BlockCopolymer—BA

Functional equivalent Compound Scale Ratio Weight G weight mMoles δ mlpoly-5-MOX 850.0 1.0 850.000 1973.32 430.75 1.200 708.3 T12 0.0 0.731631.55 1.16 1.066 0.7 Isophorone 0.115371 98.065 111.60 878.72 1.04993.5 diisocyanate PEO-400 0.210812 179.190 200.00 895.95 1.011 177.2 T120.00068 0.578 631.55 0.92 1.066 0.5 FOX DP 8 expected yield grams1128.565 expected yield, pounds 2.483 expected volume, I 0.980 expectedvolume, gal 0.259 theoretical isocyanate 0.472 titration value, mmol/gactual Isocyanate 0.483 value grams Lbs 2 incr., lbs 3 incr., lbs 4incr., lbs 5 incr, lbs Increment size: 106.25 0.23375 Charge weight:204.32 0.449494 0.683244 0.916993863 1.1507439 1.384494To a two liter 3-necked roundbottomed flask equipped with a mechanicalstirrer, addition funnel, temperature probe and control, and heatingmantle, isophorone diisocyanate (98.07 grams, 878.7 mmol isocyanate) wasadded. Monofunctional poly-5-MOX DP 8 (850 grams, 430.75 mmol OH) and0.7 grams of T12 catalyst (dibytyl tin dilaurate) was added over 90minutes maintaining a temperature of 65° C. The reaction was allowed tostir for 1 hour and a sample was removed for isocyanate titration. Anisocyanate value of 0.472 mmol of isocyanate per gram of material waspredicted based on the charge, and a value of 0.483 mmol of isocyanateper gram was found. PEO-400 was added in one portion (179.19 grams,895.95 mmol OH). The reaction was allowed to stir for 2 hours, when allthe isocyanate had disappeared by IR.

EXAMPLE 2 Synthesis of Poly-5-FOX-Diiso-Polyethylene Oxide Ether BlockCopolymer—ABA

Functional equivalent Compound Scale Ratio Weight G weight mMoles δ mlPoly-5-FOX 75.0 1.0 75.000 1140.92 65.74 1.200 62.5 T12 0.0 0.065 631.550.10 1.066 0.1 Isophorone 14.966 111.60 134.10 1.049 14.3 diisocyanatePEO-400 0.364618 27.346 200.00 136.73 1.011 27.0 T12 0.00068 0.051631.55 0.08 1.066 0.0 FOX DP 9.3 expected yield grams 117.428 expectedyield, 0.258 pounds expected volume, I 0.104 expected volume, gal 0.027theoretical isocyanate 0.759 titration value, mmol/g actual Isocyanate0.424 value grams Lbs 2 incr., lbs 3 incr., lbs 4 incr., lbs 5 incr, lbsIncrement size: 9.375 0.020625 Charge weight: 24.34 0.05355 0.0741750.094799826 0.115425 0.13605To a 250 milliliter 3-necked roundbottomed flask equipped with amechanical stirrer, addition funnel, temperature probe and control, andheating mantle, isophorone diisocyanate (14.97 grams, 134.1 mmolisocyanate) was added. Difunctional poly-5-FOX DP 8 (75 grams, 65.74mmol OH) and 0.065 grams of T12 catalyst was added over 90 minutesmaintaining a temperature of 65° C. The reaction was allowed to stir for1 hour and a sample was removed for isocyanate titration. An isocyanatevalue of 0.472 mmol of isocyanate per gram of material was predictedbased on the charge, and a value of 0.483 mmol of isocyanate per gramwas found. PEO-400 was added in one portion (27.36 grams, 136.73 mmolOH). The reaction was allowed to stir for 2 hours, when all theisocyanate had disappeared by IR.

Comparative coating cratering data was obtained as set forth in Example3 containing a control, a 3M nonionic fluorosurfactant, a DuPontnonionic fluorosurfactant, and a Poly-5-Fox-diiso-polyethylene oxideether, i.e. an ABA block copolymer similar to that set forth inExample 1. The coating is a solvent based nitrocellulose which has beenapplied as a drawdown on Leneta paper.

EXAMPLE 3

Compound Coating Comments 3M Nonionic fluorosurfactants FC-430 (1000ppm) poor leveling, small bubbles FC-430 (2500 ppm) defects in coatingFC-430 (5000 ppm) small bubbles FC-430 (7500 ppm) nice coating DuPontnonionic fluorosurfactant ZONYL FSO (1000 ppm) some coating contraction,some dewetting ZONYL FSO (2500 ppm) some coating contraction, somedewetting ZONYL FSO (5000 ppm) nice coating ZONYL FSO (7500 ppm) nicecoating, glossy ABA Poly-5-Fox-diiso-polyethylene oxide ether Poly FoxVYK (1000 ppm) small bubbles, good flow Poly Fox VYK (2500 ppm) adequateleveling Poly Fox VYK (5000 ppm) Excellent Coating Poly Fox VYK (7500ppm) Excellent Coating

As apparent from the above, the block copolymers of the presentinvention generally achieve better, that is less cratering and bettercoatings than the 3M

material or the DuPont material. The 3M and DuPont fluorosurfactants arestate of

the art and are commercially available.

Esterified Fluorooxetane Oligomers, Polymers, or Coopolymers

The direct reaction of a saturated or an unsaturated acid with ahydroxyl group of a fluorooxetane oligomer, polymer, or copolymer (asset forth herein and fully incorporated by reference), will yield anester linking group between the oligomer, polymer, or copolymer, and theacid hydrocarbon chain. Such ester end group containing compounds serveas effective flow, or leveling, or wetting agents, generally for solventcompositions containing various types of polymers therein. Thefluorinated oxetane oligomer, polymer, or copolymer, can be a variety ofdifferent compounds, such as those which are dihydroxyl, that is containtwo hydroxyl end groups as described herein, for example,polyhydroxylfluorooxetanes (FOX), or those which contain only onehydroxyl end group, i.e., monohydroxylfluorooxetanes (MOX). Moreover,such compounds can be copolymers when made from oxetane monomers andvarious cyclic ether monomers such as tetrahydrofuran.

The various fluorooxetane oligomers, polymers, or copolymers will havethe repeat unit as set forth in formulas 2AA and 2BB as set forth hereinwherein n, R, R_(f) are as set forth and fully incorporated byreference. Regardless of whether the oligomer, polymer, or copolymer isFOX or MOX, the repeat unit is the same. However, when the end oligomer,polymer, or copolymer is FOX, it will have the formula as set forth informulas 3A and 3B hereinabove, hereby fully incorporated by reference,wherein n is from 1 to about 6 and preferably from 1 to about 3, whereinR is hydrogen or an alkyl having from 1 to 6 carbon atoms and preferablymethyl or ethyl and R_(f) is a linear or branched alkyl group havingfrom 1 to about 10, or about 15, or about 20 carbon atoms and preferablyfrom about 1 to about 4 or about 7 carbon atoms. Such groups may beperfluorinated as set forth herein above or they may contain at least50% or 75%, desirably 85%, 90% or 95% of the hydrogen atoms replaced bythe fluorine atoms. The degree of polymerization (DP) for both FOX andMOX is from 2 or about 3 to about 50 or about 100, desirably from about4 to about 25 or about 30, and preferably from about 5 or about 8 toabout 12, or about 15, or about 20. Regardless of whether the endcompound is polyhydroxyl terminated (FOX) or monohydroxyl terminated(MOX) the R_(f) pendant groups of the oxetane oligomer, polymer, orcopolymer, or block copolymer, can generally all be the same or be twoor more different groups as described herein. That is, each R_(f) can bethe same such as for example a C₈F₁₇ group, or two more different groupswithin the same entity such as a C₈F₁₇ and a C₁₀F₂₁ end group, etc., andthe like, and generally have a large number of carbon atoms such as fromabout 6 or about 8 to about 18 or about 20 carbon atoms, and moredesirably from 10 to about 16 carbon atoms.

While the carboxylic acids can be poly or dicarboxylic acids having from2 to 10 carbon atoms, monocarboxylic acids are preferred. Saturatedcarboxylic acids can be utilized which contain from 1 to about 20 carbonatoms with from about 6 to about 10 carbon atoms preferred. Such acidsare well known to the art and include butanoic acid, pentanoic acid,hexanoic acid, octanoic acid, decanoic acid, dodecanoic acid,tetradecanoic acid, hexadecanoic acid, octadecanoic acid, and the like.The unsaturated acids are preferred and generally contain from about 2to about 24 carbon atoms, desirably from about 10 to about 22 carbonatoms, and preferably are the unsaturated fatty acids containing fromabout 16 to about 20 carbon atoms. Such unsaturated acids generally havefrom 1 to about 4 and desirably from 1 to about 3 unsaturated groups ordouble bonds. Examples of such unsaturated acids which contain a totalof 18 carbon atoms include oleic acid, linoleic acid, linolenic acid,and eleostearic acid. Arachidonic acid contains a total of 20 carbonatoms and 4 double bonds therein.

Other suitable carboxylic acids include the various lactones, i.e.internal esters, having from 4 to 10 carbon atoms with 6, i.e.caprolactone being preferred.

The reaction between the fluorooxetane oligomer, polymer, or copolymercontaining the same or mixed pendant R_(f) groups and 1 or 2 hydroxylend groups with the one or more acids such as unsaturated acids isgenerally carried out at elevated temperatures in the presence of asuitable esterification catalyst known to the art and to the literaturesuch as a weak inorganic acid, for example phosphorous acid. Otheresterification catalysts include titanium based tetrabutyl titanates.The reaction temperature is generally from about 100° C. to about 200°C. and preferably from about 125° C. to about 175° C. The amount of theesterification catalyst is generally very low as for example from about0.01 to about 0.1, or about 0.3, or about 0.5 parts by weight per every100 parts by weight of the fluorooxetane oligomer, polymer, orcopolymer. In order to ensure substantial or complete reaction, theamount of the carboxylic acid or lactone is generally an equivalentexcess based upon each hydroxyl end group such as from about 1.0 toabout 1.5. The net result is that the carboxylic acid group of the acidreacts with the hydroxyl end group of the fluorooxetane oligomer,polymer, or copolymer and through a condensation reaction forms an esterlinkage with the hydrocarbon portion of the acid extending therefrom. Inother words, a single carboxylic acid reacts with each hydroxyl endgroup of the fluorooxetane oligomer, polymer or copolymer. Suchcompounds serve as flow, wetting, or leveling agents in solutions in asmuch as they generally reduce the surface tension of compositions,especially solvent based polymer compositions such as variouspolyacrylates, various polyurethanes, various

epoxies, fluorine containing polymers, and various polyesters, andespecially alkyd resins. Alkyd resins are desirably used in varioussolvent based paints as architectural coatings. The solvents for suchcompositions are generally hydrocarbons such as mineral oil, used inarchitectural coatings and the like. A preferred end use of theimmediately above-described flow, wetting, or leveling agents is foralkyd-based paints, and the like.

The invention will be better understood by reference to the followingexample which serves to illustrate, but not to limit the presentinvention.

TABLE 1 Weight, Ingredient Ratio MW Grams Moles Pamolyn 200* 1 296.8269.71533 0.234874 Poly(3FOX(90%)-Co-L FOX 1 2128.80 500. 0.234874 (10%))H₃P0₃, 70% 0.121 82 0.332917 0.002842 *Pamolyn 200 is a mixture of oleicacid and linoleic acid. • FOX L is a mixture of fluorooxetane monomerswherein R_(f) is approximately 50% of C₈F₁₇, approximately 25% ofC₁₀F₂₁, and approximately 25% of C₁₂F₂₅ and higher compounds.

The reagents were charged to a one liter 3-necked round bottomed flaskequipped with a condenser, mechanical stirrer, nitrogen inlet andoutlet, temperature probe, and a heating mantle. The reaction mixturewas heated to 150° C., and allowed to stir for 100 hours. Conversion wasdetermined to be 70% using NMR analysis. An additional 0.33 g 70%phosphorous acid was added, and the reaction was heated to 150° C., andallowed to stir for 52 hours. Final conversion was determined to be 80%using NMR analysis.

TABLE 2 Weight, Ingredient Scale Ratio MW grams Moles pamolyn 200 4000.897 296.82 72.39906 0.243916 Poly-3-FOX 1 1471 400 0.271924 H3PO3, 70%0.0121 82 0.385433 0.00329A 500 ml 3-necked round bottomed flask was equipped with a heatingmantle. Temperature probe, mechanical stirrer, dean stark trap, nitrogeninlet and outlet, and reflux condenser. The reactor was charged with 400grams poly-3-fox DP 15.5 (0.271 moles OH), Pamolyn 200 (72.4 grams,0.243 moles) and 0.38 grams 70% phosphorous acid. The reaction wasdegassed with a slow nitrogen purge, then was heated to 150° C. for 96hours. NMR analysis confirmed 90% conversion of the OH groups. The yieldwas 426.1 grams.

TABLE 3 Substance Scale (g) Ratio Quantity (g) MW Eq mmoles δ ml Fox LMonomer fa-8* 150 1 150.00 545.22 6.0 275.12 1.5 100.0 Trifluoroethanol,solvent 0.526805 79.02 100.04 17.23 789.89 1.185 66.7 Trifluoroethanol,intiator 0.03058 4.59 100.04 1.00 45.85 1.19 3.9 BF₃THF, catalyst0.017106 2.57 139.9 0.40 18.34 1.1 2.3 Methylene chloride solvent 0.200530.08 84.93 7.72 354.12 1.35 22.3 Methylene chloride wash 0.5 75.0084.93 19.26 8.83E+02 1.35 55.55556 solvent Quench (5% NaHCO3) 0.85127.50 18.01 154.40 7.08E+03 1.00 127.5 Wash (water) 0.85 127.50 18.01154.40 7.08E+03 1.00 127.5 Theoretical Yield 155.9094 Expected yield,Low 140.3184 Expected yield, High 148.1139 Solids loading, % 59.02486Max wt % BF3THF 1.645764 (incorporated as THF) Initial Volume 195.2volume after Quench 378.2 volume after Wash 378.2 *97% R_(f) = C₈F₁₇ and3% R_(f) = C₁₀F₂₁A 500 ml 3-necked round bottomed flask was equipped with a magneticstirrer, reflux condenser, temperature probe, and addition funnel. 30.08grams of methylene chloride was added, followed by trifluoroethanolinitiator (4.59 grams, 45.85 mmoles), and BF₃THF (2.57 grams, 18.34mmoles). The reaction mixture was allowed to equilibrate at 25° C. for30 minutes. A solution of zox monomer (150 grams, 275.12 mmoles) intrifluorethanol (79.02 grams, 789.89 mmoles) was added over 1 hour. Amaximum temperature of 36° C. was observed. After 4 hours, 75 grams ofmethylene chloride was added, and the reaction was washed with 127.5 ml5% sodium bicarbonate, and 127.5 ml water. The organic phase was dried,and the solvent was removed under reduced pressure, and the Degree ofpolymerization was measured by NMR. A DP of 4.8 was observed.

TABLE 4 Substance Scale (g) Quantity(g) MW Eq mmoles density ml PolyFOXL fa-8* 50 50 2716.04 1 18.41 1.7 29.41 tyzor TBT 0.025 631.56 3.96E−051.066 0.02 Heptane 5 100.21 2.71 49.90 0.684 7.31 Stearic acid 5.24284.48 1 18.41 0.845 6.20 *polymer from Table 3A 100 mL 3-necked round bottomed flask was equipped with a magneticstirrer, temperature probe, dean stark trap, and reflux condenser. 50grams of PolyFOX L c80-56 dp 4.8 was added, then 0.025 grams of TyzorTBT (dupont), 5 grams of heptane, and 5.24 grams stearic acid. Thereaction mixture was allowed to heat to 192° C. over 3 hours and 35minutes. The reaction was continued for 10 hours, then the temperaturewas increased to 220° C. for 2 hours, then NMR was performed. NMRconfirmed the reaction was complete.

Various types of flow and wetting agents were added to an acrylicmodified alkyd resin obtained from Akron Paint and Varnish of Akron,Ohio and the results thereof are set forth in Table 5. The nonionicfluorosurfactant from 3M was FC-430. The ethoxylated nonionicfluorosurfactant from DuPont was Zonyl FSO. The PolyFOX-TJ isessentially that as set forth in Table 2 hereinabove whereas PolyFOX TLJis essentially that set forth in Table 1 hereinabove.

TABLE 5 85° SAG* Compound Gloss Resistance Leveling** Comments Control20 7 11 Poor wetting, many bubbles with haze; spotty gloss variations 3MNonionic Fluorosurfactants FC-430 (1000 ppm) 30 6 5 Defects; A widevariation in gloss, Haze FC-430 (2500 ppm) 33 5 6 A couple of defectsFC-430 (5000 ppm) 30 8 6 Nice coating FC-430 (7500 ppm) 30 10 6 Nicecoating DuPont Ethylated Nonionic Fluorosurfactant ZONYL FSO (1000 ppm)45 11 8 Crystals ZONYL FSO (2500 ppm) 30 11 9 Many large craters ZONYLFSO (5000 ppm) 23 11 9 Some craters ZONYL FSO (7500 ppm) 12.5 11 7Bernard Cells PolyFOX-TJ PolyFox TJ (1000 ppm) 23 2 6 PolyFox TJ (2500ppm) 25 5 6 Nice coating, slightly better than control PolyFox TJ (5000ppm) 29 7 9 Nice coating, better distinctness of image PolyFox TJ (7500ppm) 24 7 7 Nice Coating PolyFOX-TLJ PolyFOX TLJ (1000 ppm) 23 13 7 afew defects from bubbles or incomplete wetting of dust contaminatesPolyFOX TLJ (2500 ppm) 70 9 6 Beautiful coating but has couple of bubbledefects PolyFOX TLJ (5000 ppm) 68 10 6 Nice coating PolyFOX TLJ (7500ppm) 68 8 6 nice coating, superior distinctness of image *ASTM D 4440**NYPS leveling test blade method, Gardner Company

As apparent from the above table, the fluorinated polyoxetaneunsaturated acid esterficiation products, TLJ and TJ, improved coatingappearance. TLJ improved 85 degree gloss in particular, and both TJ andTLJ improved the general appearance of the coating.

TABLE 6 Synthesis of polyfox acrylate from acryloyl chloride FunctionalCompound Scale Weight G equivalent weight mMoles density ml poly-3-fox60.0 60.000 2575.00 23.30 1.150 52.2 Triethyl Amine 3.773 101.19 37.280.726 5.2 Acryloyl Chloride 3.163 90.51 34.95 1.114 2.8 Methylenechloride 100.00 84.93 1177.46 1.325 75.5 4-methoxy phenol 0.06 124.140.50 1.131 0.1 10% H₂SO₄ Wash 30 5% NaHCO₃ Wash 30 Dl water Wash 30Saturated NaCl Wash 15 expected yield 167.000 expected volume 154.075A 250 mL 3-necked round bottom flask was equipped with a magneticstirrer, reflux condenser, addition funnel, and temperature probe.Methylene chloride (100 mL), monofunctional poly-3-FOX (2575 hydroxylequivalent weight, 23.30 mMoles OH), and triethyl amine (3.77 grams,37.28 mMoles) were added, and the solution was allowed to stir until itwas homogeneous. Acryloyl chloride (3.16 grams, 34.95 mMoles) was addeddropwise over 10 minutes. A rapid exotherm was observed, and thesolution began to reflux. The reaction mixture was allowed to stir atroom temperature for 1 hour, then it was heated to reflux for 3 hours.The reaction mixture was allowed to stand overnight. 4-methoxy phenol(0.06 grams) was added, and the reaction mixture was quenched withdeionized water, then the organic layer was washed with 30 mL of 10%H₂SO₄, 30 mL of 5% sodium bicarbonate, 30 mL of deionized water, and 15mL saturated sodium chloride. The organic layer was dried, and thesolvent was removed. Fox acrylate (48.71) was isolated.Characterization: A14008 NMR: 98% conversion of OH groups, DP FOX 19.3,dp THF 0.7, MW 3763, 13.6% cyclic tetramer. GPC: Mn 1410, Mw 3040, Mw/Mn2.16.

Anionic Functionalized Polyfluorooxetanes

The polymers such as those made from various cyclic ethers, for example,oxetane, oxirane, or copolymers thereof, with another cyclic ether orwith a polyester such as those set forth herein below, often contain ahydroxyl or acid end group. As noted above, such end groups can becovalently bonded to a polar end group such as an anion for examplecarboxylate, sulfonate, sulfate, phosphate, or nitrate, and anappropriate countercation; or a cation such as ammonium, etc., and anappropriate counteranion; or a nonionic end group, etc. in a manner,e.g. as set forth in any of the different routes noted herein above. Forexample, sulfuric acid can be added to a hydroxyl end group to convertthe same to a sulfate anion. Subsequently, a countercation can be addedthereto. The reaction temperature for the anionic reaction is generallyfrom about minus 20° C. to about 50° C. and desirably from about minus5° C. to about 15° C. whereas the reaction temperature for addition ofthe counteranion is generally from about 0° C. to abut 60° C. anddesirably from about 15° C. to about 40° C.

EXAMPLES A–D Anionically Functionalized Poly5Fox

Synthesizing Covalently Bonded Anion-Cation Terminated Polyoxetanes

The poly diol poly(3-pentafluoropropoxymethyl-3-methyloxetane) (200.0 g,HEW 860.6, 0.2325 mole OH, 1.0 eq) and solvent (tetrahydrofuran) 200.0 gwere introduced into a flask at 50wt % solids and allowed to stir at 0°C. Fuming sulfuric acid (26.9 g, 0.2866 mole, 1.23 eq) was then drippedinto flask at a rate to keep the temperature below 15° C. The reactionwas followed by end group analysis which was performed by proton NMR andby an ammonium hydroxide titration to a bromothymol blue endpoint. Oncethe conversion exceeded 80–85%, the acid ends and excess acid wereneutralized by 28 wt % aqueous ammonium hydroxide (31.6 g, 0.2524 mole,1.1 eq) while maintaining a temperature below 20° C. The solution pH wasfollowed by pH paper or pH meter to a pH of 7–8. The solution wasallowed to stir at 0° C. for two hours to allow for complete saltformation. Salts were removed by vacuum filtration. The solution wasthen subjected to rotating evaporation until all of the solvent andwater was removed.

EXAMPLES E–H Anionically Functionalized Poly3Fox

Synthesizing Covalently Bonded Anion-Cation Terminated Polyoxetanes

The poly diol poly(trifluoroethoxymethyl-3-methyloxetane) (3524.0 g, HEW715.02, 4.93 mole OH, 1.0 eq) and solvent (tetrahydrofuran) 200.0 g wereintroduced into a flask at 50wt % solids and allowed to stir at 0° C.Fuming sulfuric acid (854.73 g, 9.11 mole, 1.85 eq) was then drippedinto flask at a rate to keep the temperature below 15° C. The reactionwas followed by end group analysis which was performed by proton NMR andby an ammonium hydroxide titration to a bromothymol blue endpoint. Oncethe conversion exceeds 80%–85% the acid ends and excess acid wasneutralized by 25.2 wt % aqueous ammonium hydroxide (708.23 g, 5.09mole, 1.03 eq) while maintaining a temperature below 20° C. The solutionpH was followed by pH paper or pH meter to a pH of 7–8. The solution wasallowed to stir at 0° C. for two hours to allow for complete saltformation. Salts were removed by vacuum filtration. The solution wasthen subjected to rotating evaporation until all of the solvent andwater was removed.

The above-noted polymers were then tested with regard to surface tensionin a solution of water or a water-methanol mixture and the results areset forth in Table A.

TABLE A Wt % Surface Wt % Added Tension Sample Sample Methanol (mN/m) A(Poly-5-FOX)_(n)(OSO₃)₂(NH₄ ⁺)₂ 1 0 26.2 ± 0.2 B(Poly-5-FOX)_(n)(OSO₃)₂(NH₄ ⁺)₂ 0.1 0 26.1 ± 0.2 C(Poly-5-FOX)_(n)(OSO₃)₂(NH₄ ⁺)₂ 1 0.3 25.3 ± 0.1 D(Poly-5-FOX)_(n)(OSO₃)₂(NH₄ ⁺)₂ 0.1 0.03 26.3 ± 0.2 E(Poly-3-FOX)_(n′)(OSO₃)₂(NH₄ ⁺)₂ 1 0 28.7 ± 0.1 F(Poly-3-FOX)_(n′)(OSO₃)₂(NH₄ ⁺)₂ 0.1 0 29.2 ± 0.1 G(Poly-3-FOX)_(n′)(OSO₃)₂(NH₄ ⁺)₂ 1 0.3 27.3 ± 0.1 H(Poly-3-FOX)_(n′)(OSO₃)₂(NH₄ ⁺)₂ 0.1 0.03 29.1 ± 0.2 n = 7.0,M_(w)/M_(n) = 1.55–1.75. n′ = 7.2, M_(w)/M_(n) = 1.44–1.65.

As apparent from Table A, the short R_(f) carbon atom polyoxetanescontaining polar end groups had good surface tension values in water.According to the present invention, at a 0.1% by weight concentration inwater of the low carbon atom fluorinated R_(f)-polar polyoxetanes,surface tension values can range from about 15, or about 20, or about 25to about 30, or about 35, or about 40, or about 45 or 70, and preferablyfrom about 15, or about 20, or about 25 to about 30 or 35millinewtons/meter.

The polymers of the present invention, which contain a short chainfluorinated R_(f) group as well as one or more polar groups thereon,such as in Table A can be utilized as a wetting, or flow, or levelingagent. Accordingly, Table B relates to comparative data showing theresults of coating experiments where fluorocarbon products can be usedto eliminate cratering defects. The performance of(Poly-5-FOX)_(n)(OSO₃)₂(NH₄ ⁺)₂ wherein n is approximately 5 to 7 isnoted with regard to other commercially available fluorocarbon products.

TABLE B Crater Sample Comment A (Poly-5-FOX)_(n)(OSO₃)₂(NH₄ ⁺)₂ 75 ppmno craters B (Poly-5-FOX)_(n)(OSO₃)₂(NH₄ ⁺)₂ 300 ppm no craters C StahlPUD no additive*¹ some craters D FC129*² 250 ppm craters E Zonyl FSO*³125 ppm craters F Zonyl FSO*³ 250 ppm small craters G Zonyl FSO³ 500 ppmsmall craters *¹The PUD is a polyurethane dispersion made by Stahl,U.S.A. *²FC129 is an anionic fluorosurfactant produced by 3M *³Zonyl FSOis a nonionic fluorosurfactant produced by DuPont

As apparent from Table B the surfactant of the present invention yieldedno craters meaning that good flow, wetting, and leveling properties wereobtained.

EXAMPLE 1 Anionic Functionalized Poly-5-FOX DP 2 Monofunctional

Synthesizing Covalently Bonded Anionic-Cationic Terminated Polyoxetane

Quantity Quantity, Substance Scale Ratio (g) Pounds MW Eq moles δ mlpoly-5-fox monofunctional 50 1 50.00 662.02 1 0.08 1.15 43.48Tetrahydrofuran 1 50.00 72.11 9.18 0.69 0.71 70.82 fuming sulfuric acid40.31 93.34 1.50 0.11 1.90 21.22 aqueous ammonia (concentrated, 68.2817.04 14.87 1.12 0.9 75.87 14.8 moles/liter), 30% excess Water 42.64

-   1. Charge mono-ol and THF to a 500 ml jacketed reactor with paddle    stirrer, thermometer and addition funnel.-   2. Cool with chiller bath to −5 c.-   3. Slowly add fuming sulfuric acid via addition funnel, keeping the    temperature range of −5 c to 15 c.-   4. Once all of the acid is in let stir 15 minutes.-   5. Check conversion of alcohol to sulfate by NMR, 400 MHz in CDCl3.    Continue to add acid until conversion is >98% conversion of the    alcohol.-   6. Set up a 1 liter jacketed reactor with paddle stirrer,    thermometer and addition funnel.-   7. Charge ammonium hydroxide to the 1 liter reactor and cool to −5    C.-   8. Slowly add the sulfate solution to the ammonium hydroxide keeping    the temperature range of −5 C to 40 C.-   9. A white salt ppt will form.-   10. Once all of the sulfate solution is in, check the pH of the    1-liter reactor. Range pH=9–10.-   11. Add water to dissolve salts.-   12. Phase separate and keep to product in the top organic THF    solution and discard the aqueous bottom phase.-   13. This product can be stripped of THF later and formulated as    needed.

EXAMPLE 2 Anionic Functionalized Poly9FOX

Synthesizing Covalently Bonded Anion-Cation Terminated Polyoxetane

The following ingredients were utilized

Quantity Substance (g) MW Eq moles Density ml (Poly-9-FOX) 1600.00761.87 1 2.10 1.15 1391.30 Tetrahydrofuran 1600.00 72.11 10.57 22.190.71 2266.29 Fuming sulfuric acid 1120.90 93.34 1.50 3.15 1.90 589.95Aqueous ammonia, 14.8 M, 30% 1898.71 17.04 14.87 31.22 0.9 2109.68excess Total acid equivalents 5.718 weight % ammonia used 25.20%Percentage SO3 in oleum 22.50% Theoretical polymer yield 1803.90 MolesSO₃ 0.63 Expected yield, High 1713.7041 NaHCO₃ required 52.93 toneutralize all SO3 Expected Mn 1717.91 mL Gallons volume, reaction4247.54 1.12 volume, ammonia neutralization 6357.22 1.67830 Ammoniaconcentration, moles/liter 14.8 DP of polyol 4.19-fox dp 4.1 (1600 grams, hydroxyl equivalent weight=761.9 grams per molOH, 2.1 Mol OH) was dissolved in 1600 g tetrahydrofuran (50% solids).The solution was cooled to −5° C. Fuming sulfuric acid 20% was addedover 1 hour (1120.9 grams, average MW=93.35, 3.15 Mol SO3, 1.5equivalents SO3, 5.7 equivalents acid). The exotherm did not exceed 15°C. Upon completion of addition, the exotherm subsided to a temperatureof 6–8° C. an additional 1050 grams of THF was added to keep the productin solution. Proton NMR indicated 99% conversion. The solution wascooled to −6° C., and the acidic solution was added to concentratedaqueous ammonia (1898.71 G, 31.22 Mol Ammonia), and 1200 grams deionizedwater maintaining a solution temperature below 46° C. Separate andremove the aqueous phase and Transfer THF/fox NM solution todistillation pot. Aqueous 5% NaHCO₃ (486.77 grams, 1.5% based ontheoretical NM amount) was added to the solution. The THF/water solventwas removed from the product under reduced pressure, keeping thetemperature below 47° C. pH was 9–12. The THF distillation was stoppedwhen THF content was less than 0.22 weight percent. Butyl carbitol (1165grams, 21.55 weight percent), Methanol (1171 grams, 21.66 weightpercent) and water (1437 grams, 26.59 weight percent) was added, and themixture was allowed to stir for 15 minutes.

EXAMPLE 2 Ionic Functionalized Poly-9-MOX

Synthesizing Covalently Bonded Anion-Cation Terminated Polyoxetane

Quantity Substance (g) MW Eq moles Density ml poly-9-fox monofunctional20.00 1388.42 1 0.01 1.15 17.39 sulfamic acid 10.20 97.07 7.29 0.11 1.905.37 Pyridine 8.31 79.10 7.29 0.11 0.978 8.49 Tetrahydrofuran 20.0072.11 19.25 0.28 0.71 28.33 aqueous ammonia 25.55 17.04 29.17 0.42 0.928.39 (concentrated) mL volume, reaction 51.09 Ammonia concentration,14.8 moles/literA 125 ml jacketed 3-necked flask was equipped with a reflux condenser,mechanical stirrer, and temperature probe. Poly-9-FOX polyol (20 g, 14.4mMoles OH), and sulfamic acid (10.2 grams, 105.1 mMoles) were added, andthe reaction was allowed to heat up to 90° C. Pyridine was added (8.30grams, 0.1051 mMoles). The reaction mixture was allowed to stir for 4hours at 90° C. The reaction was cooled to 25° C., and 20 grams of THFwas added. Concentrated aqueous ammonia was added (25.55 grams, 0.42moles), and the solution was filtered. The solvent was removed and 24.4grams of Poly-9-FOX ammonium sulfate was isolated.

Cationic Functionalized Polyfluorooxetanes

In a manner similar to that set forth herein above, various cations canbe directly covalently bonded to fluorooxetane oligomers, polymers, orcopolymers (mono or polyhydroxyl terminated); or bonded to blockcopolymers (mono or poly hydroxyl terminated) derived from polymerizingfluorooxetane monomers onto an alkylene oxide initiator oligomer,polymer or copolymer, or from polymerizing alkylene oxide monomers ontoa fluorooxetane oligomer, polymer, or copolymer. The manner ofpreparation of such fluorooxetane oligomers, polymers, copolymers (e.g.made with a cyclic ether monomer such as tetrahydrofuran), or blockcopolymers, is described elsewhere within this specification and ishereby fully incorporated. Thus, repeat units of the fluorooxetanemonohydroxyl or polyhydroxyl terminated oligomers, polymers, orcopolymers, or block copolymers of the same with a polyether, will havethe following repeat units

wherein n is from 1 to about 6 and preferably 1 to about 3, wherein R ishydrogen or an alkyl having from 1 to about 6 carbon atoms andpreferably is methyl or ethyl, wherein DP is from 2 to about 50 or about100 and desirably from about 4 to about 15, about 20, or about 30 andR_(f) is a linear or branched alkyl group having from 1 to about 10, orabout 15, or about 20 carbon atoms and preferably from about 1 to about4 or about 7 carbon atoms. The R_(f) groups can be perfluorinated as setforth herein above or they can contain at least 50% or 75%, desirably atleast about 90% or 95% of the hydrogen atoms replaced by the fluorineatoms. The R_(f) pendant groups of the oxetane oligomer, polymer, orcopolymer, or block copolymer, can generally all be the same or be twoor more different groups as described herein. That is, each R_(f) can bethe same such as for example a C₈F₁₇ group, or two more different groupswithin the same entity such as a C₈F₁₇ and a C₁₀F₂₁ end group, etc., andthe like. When the fluorooxetane oligomer, polymer, or copolymer, orblock copolymer contains a mixture of different pendant R_(f) groups,they generally have a large number of carbon atoms such as from about 6or about 8 to about 18 or about 20 carbon atoms, and more desirably from10 to about 16 carbon atoms.

In order to form a cationic group covalently bonded to the hydroxyl endgroup of a fluorooxetane oligomer, polymer, or copolymer, or blockcopolymer, etc., initially the hydroxyl group is reacted with afluorinated hydrocarbyl (e.g. alkyl, aromatic, etc.) sulfonic anhydride.The oligomer, polymer, copolymer, or block copolymer containing afluorinated hydrocarbyl sulfonic end group thereon is subsequentlyreacted with a very nucleophilic compound such as a tertiary amine. Theend result is a cationic end group covalently bonded through an oxygenatom (of the prior hydroxyl group) to the fluorooxetane oligomer,polymer or copolymer, or block copolymer. Naturally, an anion counterion is generally associated therewith in an aqueous solution.

The fluorinated hydrocarbyl sulfonic anhydride can generally berepresented by the formula

wherein R¹ and R² can be the same or different and are a hydrocarbylgroup such as a linear or branched alkyl having from 1 to about 15carbon atoms and preferably from about 1 to about 5 carbon atoms, or anaromatic, or an alkyl aromatic, etc. have a total of from 6 to about 15carbon atoms, with a minimum of 50%, desirably at least 75%, andpreferably at least 90% or about 95% of the hydrogen atoms replaced witha fluorine atom and preferably is perfluorinated. A preferredfluorinated alkyl sulfonic anhydride is trifluoromethane sulfonicanhydride.

Another compound which can add sulfonyl groups to the hydroxylterminated oligomer, polymer, copolymer or block copolymer are thevarious hydrocarbyl sulfonyl halide compounds where in the hydrocarbylgroup is an alkyl having from 1 to about 15 carbon atoms or an aromatic,or an alkyl aromatic, etc. having from 6 to about 15 total carbon atoms.A preferred aromatic sulfonyl halide is paratoluene sulfonyl halide.

The reaction temperature of the hydrocarbyl sulfonyl halide or thefluorinated hydrocarbyl sulfonic anhydride such as fluorinated alkylsulfonic anhydride is generally carried out at a very low temperature,such as from about 0° C. or about minus 15° C. to about minus 30° C. orabout minus 40° C. Generally a tertiary amine catalyst can be utilizedsuch as tertiary amines wherein the alkyl group can be the

same or different and is from about 1 to about 5 carbon atoms such astrimethyl amine, triethyl amine, and the like. The mole amount ofcatalyst utilized is generally from about 1.0 to about 2.0 and desirablyfrom about 1.2 to about 1.7 per mole of hydroxyl end group of theoligomer, polymer, copolymer, or block copolymer. The mole ratio of thesulfur containing compound such as the fluorinated alkyl sulfonicanhydride or paratoluene sulfonyl chloride to the hydroxyl groups of thefluorinated oxetane oligomer, polymer, or copolymer is generally fromabout 1.20 to about 2.0, and desirably from about 1.40 to about 1.60, sothat complete reaction of all hydroxyl end group occurs.

After completion of the reaction, the amine catalyst is neutralized withan acid such as hydrochloric acid and the organic layer is separated.The organic layer is then washed with water and brine to extract excessreaction products and byproducts with the sulfur fluorooxetane oligomer,polymer, or copolymer, or block copolymer being subsequently dried andfiltered.

A nucleophilic amine such as a tertiary amine is then added to the aboveproduct and reacted therewith at temperatures of from about 0° C. to thereflux temperature of the solvent, desirably from about 0° C. to about150° C., and preferably from about 20° C. to about 50° C. The reactionproduct is then filtered to remove any salts, and the solvent is removedsuch as under reduced pressure.

The end product is generally then dissolved in water. Suitable tertiaryamines include cyclic amines such as N-methylpiperazine,N-methylpyrrolidone, diazabicyclo(2,2,2)octane (DABCO) and the like.Also, various branched tertiary amines can be utilized containing analkyl group having from 1 to 4 carbon atoms wherein the various alkylgroups can be the same or different. Examples of such tertiary aminesinclude trimethyl amine, triethyl amine, tripropyl amine, and the like.

The end result is a fluorooxetane oligomer, polymer, or copolymer, orblock copolymer having an NR⁴⁺ group covalently bonded to the oxygenatom of the previous existing hydroxyl end group. R⁴ is a hydrogen,alkyl, aromatic, or combinations thereof having a total of from 1 to 12carbon atoms with an alkyl including cyclic alkyl compounds having from1 to 6 carbon atoms being preferred. In a similar manner other cationscan be added to the fluorinated oxetane compound be it ammonium,phosphonium, and the like. The preferred compound containing a cationend group is the above noted block copolymer of a fluorooxetaneoligomer, polymer, or copolymer having at least one polyether blockcopolymer bonded thereto, or to the above noted polyether blockcopolymer having at least one fluorooxetane oligomer, polymer orcopolymer block bonded thereto. Such compounds serve as flow, wetting,or leveling agents for polymers in various aqueous solutions. Examplesof suitable water dispersible, emulsifiable, or water soluble polymersare known to the literature as well as to the art and includepolyacetates, various polyacrylates, various polyacrylic acids, variouspolyesters, various polyethers, various polyurethanes, and the like. Theamount of the polyfluorooxetane-polyether block copolymer additive isgenerally from about 0.0005 or about 0.005 to about 0.5 or about 1.0 orabout 3.0 or about 5.0 parts and desirably from about 0.01 to about0.025 parts by weight for every 100 parts by weight of the watersoluble, dispersible, emulsifiable, polymers.

The addition of a cation covalently bonded to a fluorooxetane oligomer,polymer or copolymer, or block copolymer (mono or polyhydroxylterminated) will be better understood by reference to the followingexamples which serve to illustrate, but not to limit, the presentinvention. A Poly-Fox-THF-polyethylene oxide (B-A-B) diol was used asobtained in a manner similar to above-noted Example K.

EXAMPLE 1

Mole Volume, Ingredient Scale Weight g MW Moles Ratio Density mLPoly-5-Fox-THF- 86.37 86.37 1198.98 0.07 1.00 1.02 84.35 PolyethyleneOxide (B-A- B) Diol Triethyl Amine (catalysts) 10.93 101.19 0.11 1.500.73 15.06 Methylene chloride 68.27 84.93 0.80 11.42 1.33 51.33Trifluoromethane sulfonic 30.49 282.13 0.11 1.50 1.677 18.18 anhydride10% HCL wash 345.48 36.46 0.20 2.83 1 345.48 Ice water wash 345.48 18.0119.18 266.29 1 345.48 Saturated Sodium 345.48 18.01 chloride wash, ifnecessary DABCO 7.29 101.19 0.07 1.00 0.728 10.01 Volume, reaction168.89 Dp of polyol 6.00 MW of initiator 993.00The polymer solution from stage I was placed into a 500 mL 3-neckedround bottom flask, and triethyl amine (10.93 grams, 0.11 moles) wasadded. The reaction temperature was cooled to minus 30° C., and slowdropwise addition of trifluoromethane sulfonic anhydride. A maximumtemperature of minus 15° C. was observed, along with very highviscosity. After 30 minutes, 20 grams additional methylene chloride wasadded, and NMR analysis was performed. NMR analysis indicated thereaction was complete. The reaction was quenched with 345 grams of 10%HCL, and the organic layer was separated and-washed with 345 grams ofwater, and 345 grams of saturated sodium chloride. The organic layer wasdried, and filtered, and crystalline DABCO was added (Air Products,12.16 grams, 0.108 moles, 1.5 equivalents). The reaction was heated toreflux overnight. After 54 hours, the reaction was filtered to removesalts, and the solvent was removed under reduced pressure to give aviscous yellow oil. 15 grams of the cationic sample (0.3 weightfraction) was formulated with 17 grams of butyl carbitol (0.34 weightfraction), and 19.75 grams of water (0.395 weight fraction) to give aclear solution. The product formed a cloudy solution when dissolved inwater and contained a cation end groups.

Mole Volume, Ingredient Scale Weight g MW Moles Ratio Density mLPoly-5-fox diol 50 50.00 1453.00 0.03 1.00 1.02 48.83 Triethyl Amine5.22 101.19 0.05 1.50 0.73 7.19 tetramethylhexanediamine 0.59 172.320.00 0.10 1.00 0.59 methylene chloride 102.29 84.93 1.20 35.00 1.33 76.9p-toluenesulfonyl chloride 14.56 282.13 0.05 1.50 1.677 8.68 10% HCLwash 200.00 36.46 0.20 5.93 1 200.00 ice water wash 200.00 18.01 11.10322.71 1 200.00 Saturated Sodium chloride 200.00 18.01 wash, ifnecessary Dabco 5.91 112.18 0.05 1.50 0.728 5.30 Volume, reaction 100.68Dp of polyol 6 Yield tsofox, theoretical 55.34

EXAMPLE 2

A 250 mL 3-necked round bottomed flask was equipped with a mechanicalstirrer, reflux condenser, temperature probe, and addition funnel.Polyfox 5 diol (50 g, 34.41 mMol), triethyl amine (5.22 g, 51.6 mmol),tetramethyl hexanediamine (0.59 grams, 3.42 mMol) and 52.29 grams ofmethylene chloride were added, and the solution was cooled to 1.1° C.p-toluenesulfonyl chloride (14.56 g, 51.6 mMol) in 50 g methylenechloride was added dropwise over 20 minutes. The reaction mixture wasallowed to warm to room temperature overnight. NMR analysis of theproduct was performed, and 100% conversion of the OH to the tosylate wasobserved. The reaction was extracted in a seperatory funnel with 10%HCL, then water.

The methylene chloride polymer solution was dried with magnesiumsulfate. crystalline DABCO was added (air products, 5.91 g, 52.6 mmol),and the reaction was allowed to stir at 35° C. for 24 hours, then atroom temperature for 72 hours. The product contained quaternare ammoniumend groups.

Silicone Containing Polyfox Copolymers

Grafted copolymers are made by reacting a polysiloxane, containing atleast one hydrogen atom bonded to a silicone atom, with a monohydric(MOX) and/or a polyhydric (FOX) fluorooxetane oligomer, polymer orcopolymer. The fluooroxetane will be grafted to the polysiloxane at thehydrogen atom site thus forming a copolymer having a polysiloxanebackbone with pendant MOX and/or FOX oligomers, polymers or copolymers.These grafted copolymers can be utilized as flow, wetting, or levelingagents, or can be used to prepare a crosslinked silicone coating havingimproved oil resistance.

The polysiloxanes of the present invention will have the followingrepeat unit

wherein R¹, R² and R³ are, independently, a hydrogen or desirably analkyl having from 1 to about 20 carbon atoms, desirably from 1 to about10 carbon atoms with one or two carbon atoms, that is a methyl or ethylgroup, being preferred with the proviso that at least one of said R¹,R², or R³ groups is an alkyl. Preferably, R¹, R², and R³ are all alkylgroups. The number of repeat groups, that is n, of any polymer is fromabout 4 to about 1,000, desirably from about 4 to about 100, andpreferably from about 4 to about 20.

Such polysiloxanes are well known to the literature and to the art andare commercially available from Dow Corning and Gelest.

The monohydric or polyhydric fluorooxetane oligomers, polymers, orcopolymers which can be utilized are set forth herein above andgenerally have the repeat unit set forth in Formulas 2AA or 2BB asfollows.

wherein n, R, R_(f), and DP are set forth herein above. That is,generally n, independently, is from 1 to about 6 and preferably from 1to about 3. R is hydrogen or an alkyl having from 1 to 6 carbon atomsand preferably is ethyl or methyl. When the oligomer, polymer, orcopolymer is monohydric or polyhydric, DP is from about 2 to about 50 orabout 100, and desirably from about 3 or about 4 to about 15, or about20, or about 30. R_(f) is a linear branched alkyl group having from 1 toabout 10, or about 15, or about 20 carbon atoms and preferably is from 1to about 5, or about 7 carbon atoms. The R_(f) groups can beperfluorinated as set forth herein above or they can contain at least50% or 75%, desirably at least 80% or at least 90% or at least 95% ofthe hydrogen atoms being replaced by fluorine atoms. The R_(f) pendantgroups of the oxetane oligomer, polymer, or copolymer can contain two ormore different groups as described herein. That is, each R_(f) can bethe same such as for example a C₈F₁₇ group, or two or more differentgroups within the same entity such as C₈F₁₇ and C₁₀F₂₁ end group, etc.,and the like. When the fluorooxetane oligomer, polymer, or copolymercontains a mixture of different R_(f) groups, they generally have alarge number of carbon atoms such as from about 6 or about 8 to about 18or about 20 carbon atoms, and desirably from about 10 to about 16 carbonatoms.

A copolymer containing the above repeat units can be made of variousother monomers as set forth herein such as various cyclic compoundscontaining from 2 to about 4 or 5 carbon atoms with tetrahydrofuranbeing preferred.

The fluorooxetane oligomers, polymers, or copolymers if a polyhydricwill have a structure as set forth in Formulas 3A and 3B, or if amonohydric will have a structure as set forth in Formulas 5A and 5B asset forth herein. R¹ and R² are the residual hydrocarbon groups derivedfrom the polyol or monol initiator. In order for such oligomers,polymers, or copolymers to be reacted with the above noted polysiloxane,it is an important aspect of the present invention that the initiatorgroups contain an ethylenically unsaturated group therein. Accordingly,suitable alcohol initiators include an unsaturated monol or diol havinga total of from 3 to about 10 carbon atoms with specific examplesincluding allylic alcohol, Monohydric (MOX) fluorooxetane oligomers,polymers, or copolymers are preferred. Other than for the initiators,the fluorooxetane oligomers, polymers, or copolymers of Formulas 3A, 3B,5A, and 5B can be made in a manner as set forth in U.S. Pat. Nos.5,650,483; 5,668,250; 5,668,251; and 5,663,289, hereby fullyincorporated by reference.

The reaction between the polysiloxane and the monohydric or polyhydricfluorooxetane oligomers, polymers, or copolymers generally takes placeat temperatures from about 10° C. to about 100° C. and preferably fromabout 30° C. or about 40° C. or about 50° C. or about 60° C. Highertemperatures are generally preferred and the limit thereof is dependentupon the type of solvent utilized. Catalysts are generally desired witha platinum catalyst being preferred. The mole ratio of the fluorooxetaneoligomer, polymer, or copolymer to each hydrogen atom bonded to thesilicone atom of the polysiloxane is generally about 1.0 with a slightexcess being preferred. The grafting efficiencies are generally highsuch as at least about 80% and preferably at least 90%. Accordingly,grafted copolymers are formed wherein the unsaturated initiator of thefluorooxetane oligomer, polymer, or copolymer is covalently bonded tothe silicone atom at the prior site of the hydrogen atom. The formula ofthe grafted polysiloxane-g-FOX or MOX copolymer is thus

which relates to a reacted MOX polymer having an allylic alcoholinitiator.

The polysiloxane-g-fluorooxetane oligomers, polymers, or copolymers ofthe present invention serve as effective flow, wetting, or levelingagents in various solutions and thus can be utilized in variousdispersions, emulsions, or aqueous polymer solutions as well as invarious solvent based polymer systems. Examples of suitable polymerswhich are generally soluble in solvents are known to the literature aswell as to the art and generally include various polyesters, variouspolyacrylates, various polyurethanes, various epoxies, various alkyds,or various fluorine containing polymers, and the like. The amount ofsuch flow, leveling, or wetting agents is generally from about 0.001 toabout 2 or about 3 and desirably from about 0.01 to about 1.0 parts byweight for every 100 parts by weight of the solvent soluble polymers.

The invention will be better understood by reference to the followingexamples which serve to illustrate, but not to limit the presentinvention.

Compounds Quantity allyl-poly-3-FOX 10.92 g THF 25 mL Me2MeH p-siloxane49.5 g PCO85* 1 drop dissolved in 10 mL of THF *platinumdivinyldisiloxane complex from United Chemical TechnologiesProcedure

The allyl functionalized poly-3-FOX was synthesized and stored overmolecular sieves. 10.92 g of this material was added to a 125 mLjacketed flask that had been dried at 125° C. for two weeks thatcontained 25 mL of anhydrous THF that had been syringed into the flask.Prior to addition of the THF, molecular sieves were added along with astir bar. 49.5 g of a dimethyl, methylhydrogen siloxane containing 30 to35 mole percent Si—H was then added and the mixture stirred under N₂blanket for 60 minutes. 5 mL of a solution containing 1 drop of platinumcatalyst in 10 mL of anhydrous THF was then added and the mixture“cooked” at 50° C. for 130 minutes. 1 H-NMR showed a slow hydroxylationwas occurring so the remaining 5 mL of Pt/THF was added: The temperatureincreased to 55° C. Progress of the run was monitored by proton NMRspectroscopy as a function of the disappearance of the allyl olefin isproton resonance total reaction time.

Polar Group Terminated, Short Chain R_(f) Containing Polymers

Any of the above described polymers such as the fluorinated oxirane, thefluorinated polyacrylate, the fluorinated FOX-lactone, can contain oneor more polar groups thereon. The following examples relate to apolyoxetane having a polar group theron.

EXAMPLE J

The following is a preparation of a polyoxetane copolymer utilizing atosyl group to add an amphoteric polar end group thereto.

PREPARATION OF 3-METHYL-3-OXETANEMETHANOL

Trimethylolethane was used as receive from GEO Specialty Chemicals,Trimet Products Group, 2409 N. Cedar Crest Blvd, Allentown, Pa.18104-9733. Diethyl carbonate was used as received from Bayer IndustrialProducts Division, 100 Bayer Road, Pittsburgh, Pa. Dimethyl carbonatewas used as received from SNPE North America, New Jersey.p-Toluenesulfonyl chloride was used as received from Biddle SawyerCorporation. Potassium hydroxide and ethanol were used as received.

Into a 250 mL round bottomed flask fitted with a magnetic stirrer,thermometer, condenser, distillation head, and receiver were placed240.30 g trimethylol ethane (2.0 mol), 180.16 g dimethyl carbonate (2.0mol), and 0.20 g potassium hydroxide dissolved in 8 mL methanol. Themixture was refluxed until the pot temperature fell below 70° C., andthen the methanol was removed by distillation while keeping the headtemperature at 64° C.–66° C. (136.22 g isolated). Distillation wascontinued until the pot temperature rose to 145° C. The pressure wasgradually reduced to 27 in Hg while maintaining a pot temperature of140° C.–150° C. Rapid distillation of the product began, and 101.5 g of3-methyl-3-oxetanemethanol distilled at 115° C.–120° C. (˜49%).

Requirements: Reactor equipped with a reflux condenser and short pathdistillation setup. Requires a sophisticated short path setup withability to fractionate the oxetane from the cyclic carbonate formed inthe condensation process (with pot and head temperature readouts).

PREPARATION OF 3-METHYL-3-TOSYLMETHYLOXETANE

3-methyl-3-oxetanemethanol (100 g, 0.98 mol) was dissolved in 250 mLmethylene chloride, and a 35% solution of sodium hydroxide (143.60 g,1.08 mol)was added, and the reaction was cooled to 0° C. A solution ofp-toluenesulfonyl chloride was added (186.67 g, 0.98 mol) in 375 mLmethylene chloride was added over 1 hour. A white precipitate formedimmediately. The reaction was stirred for 10 additional hours. 1000 mLof water was added. The dichloromethane solution layer was then removed,and dried with sodium sulfate, and the solvent was removed. Yield:217.77 grams of 3-methyl-3-tosylmethyloxetane as white crystals, 87%.

From: Col. Czech. Chem. Commun. V52, p. 2057

PREPARATION OF POLY-3-FOX-CO-3-TOSYLMETHYL-3-METHYL OXETANE

Mole d Compound Ratio MW Moles Ratio (g/mL) mL Scale 3-FOX 50.0 1.0184.15 0.27 11.31 1.150 43.5 3-p-toluensufonyl-3- 0.5 256.08 0.09 3.751.200 methyloxetane Methylene Chloride 0.53 84.93 0.46 18.99 1.330 29.1Neopentyl Glycol 0.12498 104.15 0.06 2.50 1.017 6.1 BF₃THF 0.06715139.90 0.02 1.00 1.268 2.6 Methylene Chloride 0.8 84.93 0.47 19.62 1.33030.1 7.5% sodium bicarbonate 0.8 84.01 0.04 1.49 1.000 40.0 Water 0.8518.01 2.36 98.33 1.000 42.5 Theoretical Yield (g) 57.98 Expected Yield,Low (g) 52.18 Expected Yield, High (g) 55.08 Solids Loading reaction, %69.22 solids Loading wash, % 47.27 mL Initial Volume 72.20 Volume afterquench, mL 142.27 Volume after wash, mL 144.77

To a 250 mL 3-necked round bottomed flask was added neopentyl glycol(6.25 grams, 0.06 moles), 29 mL methylene chloride, and BF₃THF (3.36 g,0.02 moles). 3-FOX monomer (50 g, 0.27 moles), and3-p-toluenesulfonylmethyl-3-methyloxetane (23.05 g 0.09 mol) were addeddropwise over 40 minutes. After two hours, proton-NMR analysis indicatedpolymerization of the oxetane monomer was complete with a degree ofpolymerization of 6. 80 grams of methylene chloride was then added, andthe polymer solution was washed with water until a neutral pH wasobtained. Final yield was 57.98 grams, the oxetane degree ofpolymerization was 6, and the hydroxyl equivalent weight was 608.8.

Sulfate Functionalization of poly-3-FOX-co-3-tosylmethyl-3-methyloxetane with Fuming Sulfuric Acid and Amphoteric Polymer Preparation

The copolymer was reacted in the following manner to form an amphotericend group with the nonFOX polymer containing an —NH₃ ⁺ group therein.

-   1. Dissolve 50 grams of difunctional    poly-3-FOX-co-3-p-toluenesulfonylmethyl oxetane DP 6 (hydroxyl    equivalent weight=608.8 grams per mol OH, 0.08 Mol OH) in 50 g    tetrahydrofuran (50% solids). Cool the solution to 0° C.-   2. Add 18.34 grams of 20% fuming sulfuric acid (average MW=93.58,    0.20 Mol acid, 2.38 equivalents). Do not allow exotherm to exceed    15° C. Upon completion of addition, allow exotherm to subside to a    temperature of 6–8° C., then stir for 1 hour at 25° C.-   3. Continue heating until a conversion of 85%+ is obtained.-   4. Neutralize the acid with concentrated aqueous ammonia,    maintaining a solution temperature below 20° C., (13.78 g, 0.23 mol    ammonia). Follow the solution pH with pH paper or a pH meter, and    add additional ammonia as necessary until a solution pH of 7–8 is    obtained, again do not allow exotherm to exceed 20° C.-   5. After two hours at 0° C., vacuum filter to remove salts.-   6. Remove the THF/water solvent from the product under reduced    pressure.

Utility

The various noted fluorinated polar polymers of the present inventionunexpectedly functioned as wetting agents, or flow agents, or asleveling agents in a variety of aqueous and non-aqueous coatings.Examples of aqueous coatings include latex paints and floor polishesthat are applied to glass, wood, metal, ceramic and polymericsubstrates. Examples of non-aqueous or solvent-based coatings includeenamels and varnishes that are applied typically to the sameaforementioned substrates. Furthermore, the various noted fluorinated,polar polymers are effective as wetting, flow or leveling agents invariety of powder and radiation-curable coatings The noted fluorinatedpolar polymers function by lowering the surface tension of the coatingbelow that of the substrate onto which they are applied.

The various fluorinated polar polymers also can be utilized as anadditive for various consumer products, for example cleaners, shampoos,cosmetics, etc., and also as cleaners for furniture, glass, car polish,and the like.

Moreover, fluorinated polar polymers of the present invention can beutilized in coatings on various substrates to form a laminate.

Still other end uses can be categorized as follows.

For paints and coatings for improved wetting, improved leveling andgloss, as a flow rheology modifier, for improved anti-soiling, and as aTeflon wetting aid.

As waxes and polishes for improved leveling and gloss, for improvedwetting, and as a Teflon wetting aid.

For aqueous adhesives for improved wetting and leveling, with asemi-release additive, as well as nonaqueous adhesives.

For various graphic art applications for improved leveling, decreasedink wicking, for photo emulsion wetting, and for improved cylinder life.

For various polymer technology applications such as a mold releasespray, emulsion polymerization, for anti-fog, as an external lubricant,as an internal lubricant, as a coupling agent, as a Teflon wetting aid,as wetting agents for olefins and acrylics, and for CaSO₄ scale removal.

For electronic applications such as zinc battery scale inhibitor, and aplating bath aid.

For caulks to give improved leveling and anti-soiling.

For metal technology applications such as anti-corrosion, etch bathwetting, for cleaning and scale removal, and for degreasing.

For various cleaning applications such as hair conditioning and rinses,for alkaline cleaners, for glass cleaner and defogging, for shampoos,and for solvent degreasing.

Further uses include floor polish emulsions; electrolytic conversioncoatings; photographic processes; fluoropolymer emulsions; specialtyinks; water based coatings; solvent based coatings; electronic etchbaths; corrosion inhibitors; soldering systems; alkaline systems; andplastic preplate etchants.

End Use Applications and Data

A desired end use for the fluorinate containing polymers of the presentinvention is used as an additive in a floor polish composition orformulation.

Floor polish formulations are aqueous emulsions and comprised typicallyof polyolefin wax emulsions, alkali soluble resins typically of thestyrene-acrylic copolymer type, short chain acrylic polymers orcopolymers, plasticizers, biocides, water, variety of coalescingsolvents typically of the glycol ether type and defoamers typically ofthe silicone surfactant type. Floor polish formulations are typically inthe pH range of 8–10. A wetting, flow, or leveling agent, typically of afluorosurfactant type, is added to impart a high gloss finish to thedried coating.

Floor Polish Composition Preparation (Bench Scale)

Floor polish samples for bench scale testing were mixed in 100 gquantities in glass jars with 120 g capacity. A magnetic stir bar isplaced into the glass jar and the jar is placed on a balance. De-ionizedwater is added in a range of 30–50 g. A permanent plasticizer is addedin a range of 1 g–4 g. Tributoxy ethyl phosphate is a common plasticizerused in floor finish. A glycol ether or mixture of glycol ethers areadded in a range of 1 g–7 g. The sample is then placed on a stir plateand allowed to stir for 15 minutes. The jar is then placed on to abalance. Styrene-Acrylic copolymer or similar polymer blends are addedin a range of 20 g–50 g. The sample is then returned to the stir plateand allowed to mix for 30 minutes. The mixture is placed on to abalance. Polyethylene and/or polypropylene wax emulsions, alkali solubleresins, short chain acrylic copolymers, and/or blends of thesesubstances are added in a range of 0 g–15 g. At this time 150 ppm activePolymer 6A or Polymer 6B are added to the mixture. The mixture isallowed to stir for at least 2 hours. The sample is then allowed toequilibrate for 24 hours at room temperature.

where n=6–8, and where R¹ is the diol initiator.

Floor Polish Composition Preparation (Commerical Scale)

Commercial scale production of floor polish containing the followingcomposition is accomplished typically in 3000 gallon batches. 11,017 lbsof deionized water is added to a 3,000 gallon vessel. A plasticizer,such as tributoxyethyl phosphate, is added at 750 lbs along with acoalescing solvent, such as diethylene glycol monoethyl ether, at 750lbs, a bacteriostat, such as Proxel GXL (from Imperial ChemicalIndustries) at 25 lbs, and an antifoam, such as SAG 1010 (from UnionCarbide Corp.) at 5 lbs. This mixture is allowed to stir for severalhours at room temperature. At this time, the polymeric ingredients areadded to the vessel. Typically, this would consist of the addition of11,250 lbs of a styrene-acrylic copolymer and 1250 lbs of a polyethyleneemulsion. The wetting, flow, or leveling agent of Polymer 6A or 6B isthen added (12.5 lbs @ 30 wt % active ingredient). The final mixture isallowed to stir for several hours and then allowed to equilibrate for 24hours at room temperature.

EXAMPLE Laboratory Testing of Floor Polish

Laboratory testing of floor finish applications were preformed using theabove described bench scale composition in accordance with ASTM D-1436.The polish is applied to a gauze pad with an automated pipette for acoverage rate equivalent to 2000 sq. feet/gallon of floor finish. Inaddition to room temperature, the floor finish is applied underdifferent temperatures and humidities. The finish is applied at ahumidity range of 20% RH to 80% RH. The finish is applied at temperatureranges of 55° F.–95° F. The finish is then reapplied with fouradditional coats. After drying, the finish is observed to be free ofsurface defects and dries to a high gloss. Very little or no foam wasobserved when the composition of polymers 6A and 6B were tested.

Following ASTM D-2047, floor finish made with Polymers 6A and 6B do nothave a significant difference with respect to static coefficient offriction to a 95% confidence interval.

The application of a coating or paint or in this specific example, floorpolish requires a shearing action. This shearing action can introducefoam to the coating, paint or polish. If the foam is persistent, (i.e.,does not dissipate before the coating dries) undesirable optical effectsare seen such as a very rough surface that reduces the desired highgloss imparted by the coating. In addition to fluorosurfactants, othersurface active agents, such as sodium lauryl sulfate, are oftenintroduced, for example, to stabilize the polymer emulsion comprisingthe coating. Due to inherent properties of many surface active agentsadded to the coating (such as very low surface tension and/orinterfacial rheology), persistent foams are often produced. Tocircumvent this problem, defoamers are added to the composition.However, the fluorinated polymers such as Polymers 6A or 6B and thosedescribed in the present embodiment, produce little or no foam undershear with persistence times less than the drying time of the coating.In other words, the compositions are foaming resistant in that they havelow or nil foam, any foam is of short duration, and the foam breaks orcollapses before any film, layer, coating, etc. dries.

EXAMPLE Field Sample Preparation and Testing of Floor Polish

Field samples are prepared in a plastic 2 or 5 gallon containerdepending on batch size. The bucket is placed on a bench scale +/− <1%.The bucket and mixer are placed under a small horse power electric labmixer. Deionized water is added in a range of 30%–50%. The mixer isturned on low speed. The remaining chemicals are added in the samepercentages and ranges of aforementioned bench samples. Mixing times arethe same as with smaller samples. Items that are not easily measuredwithin the tolerance of the scale are weighed on a bench top balance andadded to the mixture.

An area is stripped using common industrial floor finish stripperdiluted 4:1, agitated with a 3M black floor pad, and a low speed machine(175 RPM). The floor is rinsed twice with a cotton mop and allowed todry. The bench polish composition described above is poured into a linedmop bucket. The polish is applied with a synthetic fiber string mopprovided to us under the trade name Great White which is a registeredtrademark of the ETC of the Henderson Company. The mops used have beenpreviously soaked in water overnight and wrung thoroughly beforeattaching to a mop handle and placed into the floor finish in thebucket. The mop is wrung until it is just dripping. The finish isapplied to the floor covering a section with a continuous coat. Sectionsare coated sequentially until the entire area is coated. Once the finishis completely dry, additional coats are applied until a desired gloss isobtained.

It is important to note that the aforementioned examples of floor polishformulations containing the embodiment of this patent did not containthe silicone surfactant defoamer found typically in most floor polishformulations.

Powder Coatings

The various flow or leveling agents, are wetting agents of the presentinvention, that is the low carbon atom fluorinated R_(f) group of apolyoxetane polymer or the other polymers as noted herein having eithera hydroxyl end group or another polar end group as noted herein above,for example ammonium sulfate, can be formed into powder coatingcompositions. The advantage of a powder coating composition is that itis dry and can be used in various applications without the need toevaporate solvents which are undesirable or to even evaporate water.Such powder coating compositions generally contain resin, such as apolyester, an epoxy, and the like, a crosslinker, pigments, extenders,flow aids, specific processing aids and/or a degassing compound.Components are mixed by high speed blending and then melt mixed byextrusion. The extrudate is ground to reduce particle size and thenclassified according to size. Powder coatings based on thermoformingresins do not use a crosslinker. The composition of powder coatings areknown to the literature and to the art.

The powder coating composition of Table V were made in the followingmanner.

EXAMPLE PC

Primid XL 552, a hydroxyl alkyl amide curative for acid functionalpolyester resins, is gaining wide acceptance as a replacement fortriglycidylisocyanurate (TGIC), especially in Europe. Primid XL 552cures by an esterification reaction with the elimination of water. It isa low molecular weight material with a crystalline structure. This makesit difficult to dispers in amorphous resins having a much higher meltviscosity, Whether because of the water generated during curing or thelack of complete mixing/dispersion in the resin matrix, Primid XL 552cured powders are characterized by surface defects, described variouslyas micro pinholes or micro craters, resulting in a surface “haze”,resulting in a low gloss finish and reduction in distinctness of image(DOI). The addition of the claims of this invention result in theproduction of powder coatings with much more desirable opticalproperties.

A series of eight powder coatings were prepared using conventionaltechniques: weighing/mixing, extrusion, grinding and classifying.Powders were extruded on a 50 mm twin screw extruder under the followingconditions: rear zone heat @ 100° F.; front zone heat @ 150° F., screwspeed=400 rpm; torque=70–80%. After compounding, powders were siftedthrough a 140 mesh (105 micron) screen and electrostatically sprayed ontest panels. A 4×12 inch standard Q-Panel™ (0.032 inch, ground one sidestainless steel primed substrate) was coated with each powder, sprayingthin at the top and thicker at the bottom so the effect of thickness onappearance could be more readily discerned. All coatings were cured for10 minutes at 400° F. Gloss (using a BYK Micro-Gloss meter), surfaceroughness (R_(a)) and plate flow (recommended Procedure Number 7 forInclined Plate Flow published by the Powder Coating Institute) weremeasured on the final, cured coatings.

The ingredients of the compositions are as set forth in Table V.

TABLE V (composition values are parts per hundred of resin) Panel 1 2 34 5 6 7 8 Crylcoat ™ 7617^(a) 95 95 95 95 95 95 95 95 Primid ™ XL 552 55 5 5 5 5 5 5 Resiflow ™ P-67^(c,d) 1.2 1.2 1.2 1.2 1.2 1.2 1.2 — TiO₂50 50 50 50 50 50 50 50 Benzoin 0.6 — — 0.6 0.6 0.6 0.6 0.6 FluorinatedPolymer^(e,f) — 0.2 0.4 0.2 0.4 — — 0.4 FC-430^(e,g) — — — — — 0.4 — —FC-171^(e,g) — — — — — — 0.4 — Plate flow (mm) 94 87 88 96 87 85 90 82Gloss (20°) 75.7 80 82 86.8 87.8 86 87.2 84.5 Gloss (60°) 92.8 93.8 94.594.5 94.5 94 94.5 93.8 R_(a) (μm) 0.24 0.12 0.18 0.12 0.12 0.18 0.220.19 ^(a)A hydroxyalkylamide crosslinker from UCB Chemicals Corporation.^(b)An acid functional poiyester resin from DSM. ^(c)67 wt % active onsilica carrier ^(d)A modified polyacrylate flow control agent fromEstron Chemicals, Inc. ^(e)50 wt % active on silica carrier.^(f)Fluorinated polymer (Formula 7). ^(g)Fluorosurfactants from 3M.FC-430 is a fluoroaliphatic polymeric, nonionic ester. FC-171 is aperfluoroalkylsulfonate ethoxylated of the formulaF(CF₂)₈SO₂N(C₂H₅)(CH₂CH₂O)_(~8)CH₃.

wherein n is from about 1 to about 20 with from about 5 to about 15being preferred.wherein n is from about 1 to about 20 with from about 5 to about 15being preferred.As apparent from Table V, the hydroxyl terminated flow and wetting agentof the present invention when added to the above noted powdered coatingcomposition resulted in an improved gloss, see Examples 2 through 5, incomparison with the Control, Example 1. Moreover, the powder coatings ofpresent invention generally achieve gloss values comparable to that ofcommercially available fluorsurfactants from 3M, i.e. Examples 6 and 7.

Alkoxyoxetane Monomers, and Oligomers, Polymers, and Copolymers Thereof

An alkoxyoxetane monomer is made by reacting a starting compound such asan alkyl halide-alkyloxetane with either an alkyl alcohol or an alkoxyalkyl alcohol. The alkyl halide-alkyloxetane has the following formula:

where R is a hydrogen or an alkyl having from 1 to 6 carbon atoms andpreferably from 1 to 3 carbon atoms, each R¹, independently, is an alkylhaving from 1 to 6 carbon atoms with from 1 to 3 carbons beingpreferred, and each X, independently, is a halide such as a chlorine, orbromine or an iodine atom. The compound of Formula A1A and A1B isreacted with an alkyl alcohol such as an alkoxy alkyl alcohol, e.g.HO—(R²—O—)_(n)R³ wherein R², independently, is an alkyl having from 1 toabout 6 carbon atoms and preferably from 1 to about 3 carbon atoms,wherein R³ is hydrogen, or a hydrocarbyl such as an alkyl, either linearor branched, or an aromatic, or an arylalkyl, or an alkyalkyl, etc.,having 1 to about 20 carbon atoms with from 1 to about 18 carbon atomsbeing preferred, and wherein n is 0, 1 or from 2 to about 100, andpreferably from about 0 to about 20. The resulting monomer has theformula

where R, R¹, R², R³, and n are as set forth above.

Approximately equal molar amounts of the alkyl halide-alkyloxetane, arereacted with HO—(R²—O—)_(n)R³ in the presence of a phase transfercataylst such as an alkyl ammonium halide e.g. tetrabutyl ammoniumbromide, in the presence of water at reaction temperatures of about 65°C. to about 105° C. and preferably from about 75° C. to about 85° C. Abase such as potassium hydroxide is also added to the solution. Thereaction is exothermic at high conversions, generally in excess of 75%and 85% conversion are obtained. Further addition of a base such aspotassium hydroxide is added optionally along with additional alcohol oralkoxy alcohol. The reaction is quenched with water and the organicphase separated and distilled to yield the alkoxyoxetane (A2A and A2B)monomer.

Polymerization of the alkoxyoxetanes generally occurs under essentiallythe same conditions and in essentially the same manner as polymerizationof the above noted polyhydroxyl fluorooxetane monomers or monohydricfluorooxetane monomers. Accordingly, such reaction conditions are herebyfully incorporated by reference. Such reaction conditions are also setforth in U.S. Pat. Nos. 5,650,483; 5,668,250; 5,668,251; and 5,663,289,all of which are fully incorporated by reference. By way of briefsummary, polymerization of the one or more same or differentalkoxyoxetane (A2A and A2B) monomers is initiated by either a diol toproduce a polyhydric or by a monol to produce a monohydroxyl oligomer,polymer, or copolymer. Polymerization is generally carried out insuitable solvents which are generally polar and/or halogenatedhydrocarbons having a total of from 1 to about 7 carbon atoms such asmethylene chloride, carbon tetrachloride, chloroform, trichloroethylene,chlorobenzene, ethyl bromide, dichloroethane, and the like withmethylene chloride being preferred. The amount of such solvents isgenerally from about 50 to about 100 parts by weight for every 100 partsby weight of the alkoxyoxetane monomer and the diol or monol initiator.

The one or more alkoxyoxetane monomers which are polymerized with eithera monol or diol initiator readily polymerize in the presence of theLewis acid catalyst (i.e. compounds capable of accepting a pair ofelectrons). Such suitable Lewis acids include complexes of borontrifluoride, for example BF₃ etherate, BF₃-THF, antimony pentafluoride,zinc chloride, aluminum bromide, and the like with BF₃-THF beingpreferred. When BF₃-THF was utilized, the THF will be polymerized andhence a alkoxyoxetane-THF copolymer will be produced. Generally theamount of THF within the copolymer is from about 0.05 to about 10 orabout 12 or about 30 or about 50 percent by weight and desirably from

about 0.1 to about 5 percent by weight based upon the total weight ofthe copolymer.

Polymerization is carried out at temperatures of from about 0° C. toabout 70° C. and preferably from about 30° C. to about 50° C.Polymerization times can vary with regard to the temperature and otherfactors and generally range from about 1 to about 4 hours. Once thevarious alkoxyoxetane monomers have been polymerized, the end productwhich is a copolymer solution can be washed with water to remove thecatalyst.

The polyhydric or monohydric alkoxyoxetane oligomers, polymers, orcopolymers (ROX) will have the following repeat units

where R, R¹, R², R³, and n are set forth above. The degree ofpolymerization (DP) is generally from about 2 to about 50 or about 100,and desirably from about 3 or about 4 to about 10, or about 15, or about20, or about 30. When polymerized with other additional monomers such asvarious cyclic ethers, having a total of from 2 to about 5 carbon atomsas set forth hereinabove and fully incorporated by reference with regardto all aspects thereof with tetrahydrofuran being preferred, a copolymerwill be produced.

Another embodiment of the present invention relates to polymerizingalkoxyoxetane monomers, i.e. A2A or A2B, along with fluorooxetanemonomers

such as set forth in Formulas 2AA and 2BB in the presence of the abovenoted diol initiators or monol initiators to yield copolymers such asstatistical or block. The mole amount of the alkoxyoxetane monomers canrange from about 1 to about 99 moles, desirably from about 20 to about60 moles, and preferably from about 25 to about 50 moles for every 100total moles of said alkoxyoxetane monomers as set forth in Formulas A2Aand/or A2B and said fluorooxetane monomers set forth in Formulas 2AAand/or 2BB. Depending upon whether a diol initiator or a monol initiatoris utilized, respectively, either a polyhydroxyl terminated or amonohydroxyl terminated oligomer, polymer, or copolymer will beproduced. The degree of polymerization of from about 2 to about 50 orabout 100, and desirably from about 3 or about 4 to about 10, or about15, or about 20, or about 30.

The alkoxyoxetane oligomers, polymers, or copolymers, either alone or ascopolymers with fluorooxetane oligomers, polymers, or copolymers, serveas effective flow, wetting, or leveling agents in various solutions andthus can be utilized in various dispersions, emulsions, or aqueouspolymer solutions as well as in various solvent based polymer systems.Examples of suitable water soluble, dispersible, or emulsifiable,polymers are known to the literature as well as to the art and includevarious polyacetates, various polyacrylates, various polyacrylic acids,various polyesters, various polyethers, various polyurethanes, variousfluorine containing polymers, and the like. Examples of suitablepolymers which are generally soluble in solvents are known to theliterature as well as to the art and generally include variouspolyacrylate, various polyesters, various polyurethane, various epoxies,various alkyds, or various fluorine containing polymers, and the like.The amount of such flow, leveling, or wetting agents is generally fromabout 0.001 to about 1.0 or about 3.0 and from about 0.01 to about 0.5parts by weight for every 100 parts by weight of the water soluble,dispersible, or emulsifiable polymers; and generally from about 0.001 toabout 1.0 or about 3.0 and desirably from about 0.01 to about 0.5 partsby weight for every 100 parts by weight of the solvent soluble polymers.

Generally, the same FOX, MOX, and/or FOX L reactions as set forth inthis specification including formation of various copolymers, blockcopolymers, addition of anionic end groups or cationic end groups ornonionic end groups, etc., as well as reactions with polyethers,carboxylic acids, and polysiloxanes can be carried out in essentiallythe same manner and reaction conditions as set forth herein with respectto ROX. Such reactions involve ROX oligomers, polymers, or copolymers(as well as monomers which form the same) with FOX or MOX, either asstatistical copolymers, or as block copolymers, for example (FOX)-(ROX),or (ROX)-(FOX), or (ROX)-(FOX)-(ROX), or (FOX)-(ROX)-(FOX). Accordingly,it can be seen that a great number and variety of different fluorinecontaining compounds, or surface active compounds, or flow, wetting, orleveling agents can be created.

The invention will be better understood by reference to the followingexamples which serve to illustrate, but not to limit the presentinvention.

EXAMPLE 1 Synthesis of 3(2′-methoxyethoxy-3-methyloxetane

Mole Material Weight g MW Moles Ratio Density ml Scale 2-Methoxyethanol200 200.00 76.10 2.63 1.00 1.373 145.7 3-bromomethyl-3- 455.38 165.022.76 1.05 1.435 317.3 methyloxetane tetrabutyl ammonium bromide 21.18322.37 0.07 0.025 1 21.2 Water 115.40 18.01 6.41 2.44 1.000 115.4 45%aqueous KOH 364.03 56.10 2.92 1.11 1.456 250.0 Water 184.60 18.01 10.253.90 1.000 184.6 45% aqueous KOH 8.00 56.10 0.06 0.024 1.456 5.5 Water176.60 18.01 9.81 3.73 1.000 176.6 Theoretical Yield, (g) 421.1 ExpectedYield, low (g) 315.8 Expected Yield, high (g) 400.0 Solids Loading, %36.4 KBR Concentration, Mol/l 5.3 KBR Concentration, wt % 41.0 ml Volumeafter KOH addn. 849.6 Volume after quench 1034.2 Volume after phasesplit 463.0 Volume after wash 645.1A 1 liter jacketed 3-necked roundbottomed flask was equipped with atemperature probe, magnetic stirrer, reflux condenser and additionfunnel. 2-methoxyethanol (200.00 g, 2.63 moles), BrMMO (455.38 g, 2.76moles), tetrabutyl ammonium bromide (21.18 g), and 115.4 g water wereadded. The reaction mixture was heated to 85° C. A 45% solution ofpotassium hydroxide (364.03 grams, 2.92 moles) was added over 1 hour and10 minutes. An exothermic reaction was observed. After 4 hours, 78%conversion was observed. Additional 2-methoxyethanol (44.39 g, 0.58moles) was added, followed by 80 grams of 45% potassium hydroxide. Thereaction was heated to 102° C. The reaction was quenched with water, andthe organic phase was separated and distilled. 3-(2′-methoxyethoxy)-3-methyloxetane was isolated (247.76 grams, 58%).

EXAMPLE 2 Synthesis of 3-methyl-3-methoxymethyloxetane

Mole Material Weight G MW Moles Ratio Density ml Scale Methanol 100100.00 32.04 3.12 1.00 0.791 126.4 3-bromomethyl-3- 540.80 165.02 3.281.05 1.435 376.9 methyloxetane tetrabutyl ammonium bromide 25.15 322.370.08 0.025 1 25.2 Water 57.70 18.01 3.20 1.03 1.000 57.7 45% aqueous KOH428.08 56.10 3.43 1.10 1.456 294.0 Water-quench 92.30 18.01 5.12 1.641.000 92.3 Hexane 100.00 86.17 1.16 0.37 0.655 152.7 Theoretical Yield,(g) 356.4 Expected Yield, low (g) 267.3 Expected Yield, high (g) 338.6Solids Loading, % 30.9 KBR Concentration, Mol/l 7.7 KBR Concentration,wt % 51.5 ml Volume after KOH addn. 880.2 Volume after quench 972.5Volume after phase split 503.3A 1 liter jacketed 3-necked roundbottomed flask was equipped with atemperature probe, magnetic stirrer, reflux condenser and additionfunnel. methanol (100.00 g, 3.12 moles), BrMMO (540.80 g, 3.28 moles),tetrabutyl ammonium bromide (25.15 g), and 57.7 g water were added. Thereaction mixture was heated to 85° C. A 45% solution of potassiumhydroxide (428.08 grams, 3.43 moles) was added over 1 hour and 10minutes. An exothermic reaction was observed. After 10 hours, 86%conversion was observed. The water phase was removed, and 61.15 grams of45% potassium hydroxide was added, followed by 100 ml hexane with a deanstark trap. The solution was refluxed until water no longer came off.The reaction was quenched with water, and the organic phase wasseparated and distilled. 3-methyl-3-methoxymethyloxetane was isolated.

EXAMPLE 3 Synthesis of Copolymers of alkoxyoxetane-fluorooxetanePolymers

Quantity Substance Scale (g) (g) MW Eq mmoles δ ml 3-fox Monomer 100100.00 184.15 4.8 543.04 1.15 86.96 Methoxymethyl methyl oxetane 15.49116.16 1.19 133.35 0.8 19.36 Trifluoroethanol, solvent 65.83 100.04 5.82658.03 1.185 55.55 Trifluoroethanol, intiator 11.32 100.04 1.00 113.131.19 9.55 BF₃.THF, catalyst 6.33 139.9 0.40 45.25 1.268 4.99 methylenechloride, reaction solvent 23.1 84.93 2.40 271.99 1.35 17.36 Methylenechloride wash solvent 57.75 84.93 6.01 679.97 1.35 43.42 Quench (5%NaHCO3) 100.00 84.01 0.52 59.51 1.00 100.00 Wash (water) 100.00 18.0149.08 5,552.47 1.00 100.00A 500 ml jacketed 3-necked roundbottomed flask was equipped with atemperature probe, magnetic stirrer, reflux condenser and additionfunnel. The reactor was charged with 23.1 grams of methylene chloride,trifluoroethanol initiator (11.32 grams, 113.13 mmoles), and BF₃.THF(6.33 grams, 45.25 mmoles). A solution consisting of 3-fox monomer (100grams, 543.04 mmoles), methoxymethyl methyl oxetane (15.49 grams, 133.35mmoles), and trifluoroethanol solvent (65.83 grams, 658.03 mmoles) wasprepared, and added over 1 hour and ten minutes. A rapid exotherm wasobserved, with a maximum temperature of 35° C. The reaction mixture wasallowed to stir for 16 hours at 25° C., then 100 mL 5% sodiumbicarbonate solution was added to quench the reaction. The reaction waswashed a second time with 100 ml deionized water.The solution was dried, and the solvent was removed to give 118.8 gramsof polymer, dp 6.9.

EXAMPLE 4 Synthesis of Copolymers of alkoxyoxetane-fluorooxetanePolymers

Scale Quantity Substance (g) (g) MW Eq mmoles δ ml 5-fox Monomer 100100.00 234.15 4.8 427.08 1.15 86.96 Methoxymethyl methyloxetane 12.18116.16 1.18 104.86 0.8 15.21 Trifluoroethanol, solvent 63.94 100.04 7.18639.18 1.185 55.55 Trifluoroethanol, intiator 8.9 100.04 1.00 88.97 1.197.51 BF₃.THF, catalyst 4.98 139.9 0.40 35.59 1.268 3.92 methylenechloride, reaction solvent 22.44 84.93 2.97 264.22 1.35 16.87 Methylenechloride wash solvent 56.09 84.93 7.42 660.43 1.35 41.55 Quench (5%NaHCO3) 100.00 84.01 0.52 59.51 1.00 100.00 Wash (water) 100.00 18.0149.08 5,552.47 1.00 100.00A 500 ml jacketed 3-necked roundbottomed flask was equipped with atemperature probe, magnetic stirrer, reflux condenser and additionfunnel. The reactor was charged with 22.4 grams of methylene chloride,trifluoroethanol initiator (8.9 grams, 88.97 mmoles), and BF₃.THF (4.98grams, 35.59 mmoles). A solution consisting of 5-fox monomer (100 grams,427.08 mmoles), methoxymethyl methyl oxetane (12.18 grams, 106.77mmoles), and trifluoroethanol solvent (63.94 grams, 639.18 mmoles) wasprepared, and added over 1 hour and ten minutes. A rapid exotherm wasobserved, with a maximum temperature of 35° C. The reaction mixture wasallowed to stir for 16 hours at 25° C., then 100 mL 5% sodiumbicarbonate solution was added to quench the reaction. The reaction waswashed a second time with 100 ml deionized water. The solution wasdried, and the solvent was removed to give 107 grams of polymer, dp 6.

EXAMPLE 5 Synthesis of Polyethylene Oxide Oxetane Monomer

Mole Material Weight g MW Moles Ratio Density ml Scale Carbowax 350 200200.00 350.00 0.57 1.00 1.373 145.7 3-bromomethyl-3-methyloxetane 99.01165.02 0.60 1.05 1.435 69.0 tetrabutyl ammonium bromide 4.61 322.37 0.010.025 1 4.6 Water 115.40 18.01 6.41 11.21 1.000 115.4 45% aqueous KOH78.36 56.10 0.63 1.10 1.456 53.8 Water 184.60 18.01 10.25 17.94 1.000184.6 Theoretical Yield, (g) 91.5 Expected Yield, low (g) 68.7 ExpectedYield, high (g) 87.0 Solids Loading, % 18.4 KBR Concentration, Mol/l 1.8KBR Concentration, wt % 17.9 ml Volume after KOH addn. 388.5 Volumeafter quench 573.1 Volume after phase split 214.7A 500 milliliter jacketed 3-necked roundbottomed flask was equipped witha temperature probe, magnetic stirrer, reflux condenser and additionfunnel. Carbowax 350 (200.00 g, 0.57 moles OH, 350 g/mol MW), BrMMO(99.01 g, 0.60 moles), Tetrabutyl ammonium bromide (4.61 g), and 115.4 gwater were added. The reaction mixture was heated to 85° C. A 45%solution of potassium hydroxide (78.36 grams, 0.63 moles) was added over1 hour and 10 minutes. An exothermic reaction was observed. After 4hours, 90%+ conversion of the BrMMo was observed. The Reaction wasallowed to cool to room temperature. Methylene chloride (200 grams) wasadded the reaction was quenched with 100 grams of water, and the organicphase was separated and the solvent was removed.3-methyl-3-(methoxypolyethylene glycol)oxetane was isolated (177.8grams).

While in accordance with the patent statutes, the best mode andpreferred embodiment have been set forth, the scope of the invention isnot limited thereto, but rather by the scope of the attached claims.

1. A block copolymer composition, comprising: at least onepolyfluorooxetane block bonded to a polyether block via an etherlinkage, said polyfluorooxetane block having a repeat unit of theformula

wherein each n is, independently, 1 to about 6, wherein R is hydrogen oran alkyl group having from 1 to 6 carbon atoms, and wherein each R_(f)is, independently, a linear or branched alkyl group of from 1 to about20 carbon atoms with a minimum of 50% of the hydrogen atoms of saidR_(f) alkyl group being replaced by F, and optionally up to all of theremaining H atoms being replaced by I, Cl, or Br, or each said R_(f)group, where DP is from 2 to about 100; and wherein said polyether blockhas ether repeat units that include from 2 to about 6 carbon atoms perrepeat unit, and wherein the number average molecular weight of saidpolyether block is from about 250 to about 10,000.
 2. A block copolymercomposition according to claim 1, wherein said DP is from 2 to about 30,and wherein said polyfluorooxetane block is an oligomer, a polymer, or acopolymer.
 3. A block copolymer composition according to claim 2,wherein said R_(f) contains a minimum of 75 percent of said hydrogenatoms being replaced by F.
 4. A block copolymer composition according toclaim 3, wherein the number average molecular weight of said polyetherblock is from about 300 to about 5,000, and wherein saidpolyfluorooxetane block includes one or more repeat units that derivefrom tetrahydrofuran.
 5. A block copolymer composition according toclaim 4, wherein said DP is from about 4 to about
 20. 6. A blockcopolymer composition according to claim 5, wherein n is from 1 to about3, R is methyl or ethyl, wherein said R_(f) is from 1 to about 7 carbonatoms and contains a minimum of 95% of said hydrogen atoms beingreplaced by F.
 7. A block copolymer composition according to claim 6,wherein said block copolymer is an AB, or a BAB, or a BA, or an ABAblock copolymer, wherein said A block is said polyether block and said Bblock is said polyfluorooxetane block.
 8. A flow, or wetting, orleveling agent, comprising the composition of claim
 1. 9. A flow, orwetting, or leveling agent, comprising the composition of claim
 3. 10. Aflow, or wetting, or leveling agent, comprising the composition of claim5.
 11. A flow, or wetting, or leveling agent, comprising the compositionof claim
 7. 12. A solution comprising a flow, or leveling, or wettingagent comprising the composition of claim
 1. 13. A polymer solutioncontaining a flow, or leveling, or wetting agent comprising thecomposition of claim 1, wherein the block copolymer is an aqueoussoluble, dispersible, or an emulsifiable polymer.
 14. A polymericsolution containing a flow, or leveling, or wetting agent comprising thecomposition of claim 1, wherein the block copolymer is a solvent solublepolymer.
 15. A polymeric solution containing a flow, or leveling, orwetting agent comprising the composition of claim 6, wherein the blockcopolymer is a solvent soluble polymer.
 16. A composition comprising:the reaction product of a polyether initiator and a fluorooxetanemonomer having the formula

wherein each n is, independently, 1 to about 6, wherein R is hydrogen oran alkyl group having from 1 to 6 carbon atoms, and wherein each R_(f)is, independently, a linear or branched alkyl group of from 1 to about20 carbon atoms with a minimum of 50% of the hydrogen atoms of saidR_(f) alkyl group being replaced by F, and optionally up to all of theremaining H atoms being replaced by I, Cl, or Br, wherein said polyetherinitiator has at least one reactive hydroxyl end group, repeat groupscontaining 2 or 3 carbon atoms, or combinations thereof, and a numberaverage molecular weight of at least
 250. 17. A composition according toclaim 16, wherein R_(f) has from 1 to 7 carbon atoms and a minimum of 90percent of said hydrogen atoms being replaced by F, and wherein saidpolyether initiator has a molecular weight of from about 300 to about5,000.
 18. A composition according to claim 17, further including thereaction product of said polyether initiator, said fluoroxetane monomer,and a tetrahydrofuran monomer, and wherein said polyether initiator has2 reactive hydroxyl end groups.
 19. A composition according to claim 18,wherein said reaction product is an AB or a BAB block copolymer whereinsaid A block derives from said polyether initiator and said B block isderived from said fluorooxetane monomers and said tetrahydrofuranmonomer.
 20. A composition comprising: the reaction product of apolyfluorooxetane initiator and an alkylene oxide monomer comprisingethylene oxide, propylene oxide, or mixtures thereof, wherein saidpolyfluorooxetane initiator is an oligomer, a polymer, or a copolymerhaving 1 or 2 hydroxyl end groups, and having a repeat unit of theformula

wherein each n is, independently, 1 to about 6, wherein R is hydrogen oran alkyl group having from 1 to 6 carbon atoms, and wherein each R_(f)is, independently, a linear or branched alkyl group of from 1 to about20 carbon atoms with a minimum of 50% of the hydrogen atoms of saidR_(f) alkyl group being replaced by F, and optionally up to all of theremaining H atoms being replaced by I, Cl, or Br and DP is from about 2to about
 100. 21. A composition according to claim 20, wherein R_(f) hasfrom 1 to 7 carbon atoms and a minimum of 90 percent of said hydrogenatoms being replaced by F.
 22. A composition according to claim 21,wherein said polyfluorooxetane copolymer contains repeat groups derivedfrom tetrahydrofuran, and wherein said polyfluorooxetane initiator hastwo hydroxyl end groups.
 23. A composition according to claim 22,wherein n is 1 to about 3, wherein R is methyl or ethyl, and wherein DPis from about 4 to about
 20. 24. A composition according to claim 23,wherein said reaction product is a BA or an ABA block copolymer whereinsaid A block is a polyether block and said B block is apolyfluorooxetane oligomer, polymer, or copolymer.